Synergistic compositions for inhibiting plant growth

ABSTRACT

A plant growth-inhibiting composition comprising (1)   &lt;IMAGE&gt;  (I) &lt;IMAGE&gt; (II)   &lt;IMAGE&gt; (III)   &lt;IMAGE&gt; (IV)   &lt;IMAGE&gt; (V)  or &lt;IMAGE&gt; (VI)  and (2)   &lt;IMAGE&gt; (VII)  or   &lt;IMAGE&gt; (VIII)   wherein the various radicals are as defined.

This is a division of application Ser. No. 337,648, filed Jan. 7, 1982,now U.S. Pat. No. 4,452,625.

The present invention relates to new plant growth-regulatingcombinations of certain azoles or pyrimidine butanol derivatives on theone hand and certain known phosphonic acid derivatives or1-aminocyclopropane-1-carboxylic acid derivatives on the other hand.

It has already been disclosed that numerous triazole derivatives haveplant growth-regulating properties (see DE-A (German PublishedSpecification Nos.) 2,407,143, 2,737,489, 2,906,061, 2,645,617,2,838,847 and JP-A (Japanese Published Specification) 53,130,661).However, the activity of the substances, especially when smallquantities are used, is not always satisfactory.

Furthermore, it is already known that certain pyrimidine butanolderivatives can be used for regulating plant growth (see U.S.application Ser. No. 200,170 filed Oct. 24, 1980, now pending. In manycases, however, the activity of these substances also leaves somethingto be desired.

It is further known that phosphonic acid derivatives capable of ethylenecleavage affect plant growth (see DE-A (German Published Specification)2,053,967). However, the activity of these substances is also not alwaysadequate in practice.

Finally, it has already been reported that certain1-amino-cyclopropane-1-carboxylic acid derivatives have plantgrowth-regulating properties (see U.S. application Ser. No. 192,744filed Oct. 1, 1980, now pending. However, the results achieved withthese substances are also not always completely satisfactory.

According to the present invention there is now provided a new plantgrowth-regulating composition containing as active ingredients

(1) an azole of the general formula ##STR2## in which

R¹ represents an optionally substituted aryl radical,

R² represents an alkyl or halogenoalkyl radical,

X represents oxygen or methylene and

Y represents carbonyl or a group --CH(OH)--, or an azole of the generalformula ##STR3## in which

R³ represents an optionally substituted alkyl, cycloalkyl or optionallysubstituted aryl radical,

R⁴ represents a hydrogen atom or an alkyl radical,

R⁵ represents a hydrogen atom or an alkyl, cycloalkyl, optionallysubstituted cycloalkenyl, alkenyl or optionally substituted arylradical, or

R⁴ and R⁵ together with the carbon atom to which they are bondedrepresent an optionally substituted cycloalkenyl or cycloalkyl radical,

R⁶ represents a hydrogen atom or an alkyl radical,

X¹ represents a group of the general formula ##STR4## and additionallyrepresents a keto group if

R³ represents an optionally substituted alkyl or cycloalkyl radical,

R⁷ represents a hydrogen atom or an alkyl, optionally substitutedaralkyl, acyl or optionally substituted carbamoyl radical, and

R⁸ represents a hydrogen atom or an alkyl or optionally substitutedaralkyl radical,

or an azole of the general formula ##STR5## in which

R⁹ represents an optionally substituted aryl radical,

R¹⁰ represents alkyl, halogenoalkyl or optionally substituted aryl, and

Y¹ represents carbonyl or a group --CH(OH)--,

or an azole of the general formula ##STR6## in which

R¹¹ and R¹² are identical or different and represent an optionallyalkyl-substituted cycloalkyl radical, an alkyl or halogenoalkyl radicalor a phenyl radical which is optionally substituted by halogen, alkyl,alkoxy, phenyl and/or nitro,

or an azole derivative of the general formula ##STR7## in which

R¹³ represents an alkyl, optionally substituted cycloalkyl or optionallysubstituted phenyl radical,

X² represents a nitrogen atom or a CH group,

Y² represents a grouping --OCH₂ --, --CH₂ CH₂ -- or --CH═CH--,

Z represents a halogen or an alkyl, cycloalkyl, alkoxy, alkylthio,halogenoalkyl, halogenoalkoxy, halogenoalkylthio, optionally substitutedphenyl, optionally substituted phenoxy, optionally substitutedphenylalkyl or optionally substituted phenylalkoxy radical, and

m is 0, 1, 2 or 3,

or an acid addition salt or metal salt complex of an azole of theformula (I), (II), (III), (IV) or (V), or a pyrimidine butanolderivative of the general formula ##STR8## in which

R¹⁴ represents a hydrogen or halogen atom or an alkyl or alkoxy radicalor a benzyloxy radical which is optionally substituted by halogen, and

R¹⁵ represents a hydrogen or halogen atom, and

(2) a phosphonic acid derivative of the general formula ##STR9## inwhich

R¹⁶ and R¹⁷ independently of each other represent a hydrogen atom or analkali metal cation,

or a 1-amino-cyclopropane-1-carboxylic acid derivative of the generalformula ##STR10## in which

R¹⁸ represents a hydroxyl, alkoxy, aralkoxy, amino, alkylamino ordialkylamino radical or a radical O.sup.⊖ M.sup.⊕,

M.sup.⊕ representing an alkali metal ion equivalent or alkaline earthmetal ion equivalent, or an ammonium, alkylammonium, dialkylammonium,trialkylammonium or tetraalkylammonium ion, and

R¹⁹ represents an amino radical or a radical --NH--CO--R,

wherein

R represents a hydrogen atom or an alkyl or aryl radical, and

R¹⁹ further represents a radical --N.sup.⊕ H₃ A.sup.⊖,

wherein

A.sup.⊖ represents a chloride, bromide or iodide ion, alone or inadmixture with a solid or liquid or liquefied gaseous diluent orcarrier. The new active compound combinations of the present inventionare very suitable for inhibiting plant growth.

Surprisingly, the plant-growth inhibiting action of the active compoundcombinations according to the invention is substantially higher than thesum of the actions of the individual active compounds. Thus, a realsynergistic effect, which cannot be foreseen, is present, and not onlyan extension of the action. The active compound combinations thusrepresent a valuable enrichment of the art.

The formulae (I), (II), (III), (IV) and (V) give general definitions ofthe azoles contained in the active compound combinations according tothe invention.

Preferred azoles of formula (I) are those in which,

R¹ represents a phenyl radical which is optionally monosubstituted,disubstituted or trisubstituted, the substituents being identical ordifferent and being selected from fluorine, chlorine, bromine, phenyl,phenoxy, nitro alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4carbon atoms, cycloalkyl having 3 to 7 carbon atoms, halogenoalkylhaving 1 to 4 carbon atoms and 1 to 5 halogen atoms (particularlyfluorine, chlorine and bromine atoms) and by cyano,

R² represents a straight-chain or branched alkyl radical having 1 to 6carbon atoms, or a halogenoalkyl radical having 1 to 6 carbon atoms and1 to 5 halogen atoms (fluorine, chlorine and bromine being preferred),

X represents oxygen or methylene, and

Y represents carbonyl or a group --CH(OH).

The compounds listed in the following table may be individuallymentioned as examples of azoles of the formula (I):

    ______________________________________                                         ##STR11##                    (I)                                             R.sup.1      X       Y         R.sup.2                                        ______________________________________                                         ##STR12##   O       CO        t-C.sub.4 H.sub.9                               ##STR13##   O       CO        t-C.sub.4 H.sub.9                               ##STR14##   O       CO        t-C.sub.4 H.sub.9                               ##STR15##   O       CO        t-C.sub.4 H.sub.9                               ##STR16##   CH.sub.2                                                                              CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 F                    ##STR17##   CH.sub.2                                                                              CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 F                    ##STR18##   CH.sub.2                                                                              CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 F                    ##STR19##   CH.sub.2                                                                              CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 F                    ##STR20##   CH.sub.2                                                                              CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 F                    ##STR21##   CH.sub.2                                                                              CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 F                    ##STR22##   CH.sub.2                                                                              CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 F                    ##STR23##   CH.sub.2                                                                              CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 Cl                   ##STR24##   CH.sub.2                                                                              CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 Cl                   ##STR25##   CH.sub.2                                                                              CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 Cl                   ##STR26##   CH.sub.2                                                                              CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 Cl                   ##STR27##   CH.sub.2                                                                              CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 Cl                   ##STR28##   CH.sub.2                                                                              CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 Cl                   ##STR29##   CH.sub.2                                                                              CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 Cl                   ##STR30##   CH.sub.2                                                                              CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 Cl                   ##STR31##   CH.sub.2                                                                              CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 Cl                   ##STR32##   CH.sub.2                                                                              CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 Cl                   ##STR33##   CH.sub.2                                                                              CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 Cl                   ##STR34##   CH.sub.2                                                                              CH(OH)    C(CH.sub.2 Cl).sub.2 CH.sub.3                   ##STR35##   CH.sub.2                                                                              CH(OH)    C(CH.sub.2 Cl).sub.2 CH.sub.3                   ##STR36##   CH.sub.2                                                                              CH(OH)    C(CH.sub.2 Cl).sub.2 CH.sub.3                   ##STR37##   CH.sub.2                                                                              CH(OH)    C(CH.sub.2 Cl).sub.2 CH.sub.3                   ##STR38##   CH.sub.2                                                                              CH(OH)    C(CH.sub.2 Cl).sub.2 CH.sub.3                   ##STR39##   CH.sub.2                                                                              CH(OH)    C(CH.sub.2 Cl).sub.2 CH.sub.3                   ##STR40##   CH.sub.2                                                                              CH(OH)    C(CH.sub.2 Cl).sub.2 CH.sub.3                   ##STR41##   CH.sub.2                                                                              CH(OH)    C(CH.sub.2 Cl).sub.2 CH.sub.3                   ##STR42##   CH.sub.2                                                                              CH(OH)    C(CH.sub.2 Cl).sub.2 CH.sub.3                   ##STR43##   CH.sub.2                                                                              CH(OH)    C(CH.sub.2 Cl).sub.2 CH.sub.3                   ##STR44##   CH.sub.2                                                                              CH(OH)    C(CH.sub.2 Cl).sub.2 CH.sub.3                   ##STR45##   CH.sub.2                                                                              CH(OH)    C(CH.sub.2 F).sub.2 CH.sub.3                    ##STR46##   CH.sub.2                                                                              CH(OH)    C(CH.sub.2 F).sub.2 CH.sub.3                    ##STR47##   CH.sub.2                                                                              CH(OH)    C(CH.sub.2 F).sub.2 CH.sub.3                    ##STR48##   CH.sub.2                                                                              CH(OH)    C(CH.sub.2 F).sub.2 CH.sub.3                    ##STR49##   CH.sub.2                                                                              CH(OH)    C(CH.sub.2 F).sub.2 CH.sub.3                    ##STR50##   CH.sub.2                                                                              CH(OH)    C(CH.sub.2 F).sub.2 CH.sub.3                    ##STR51##   CH.sub.2                                                                              CH(OH)    C(CH.sub.2 F).sub.2 CH.sub.3                    ##STR52##   CH.sub.2                                                                              CH(OH)    C(CH.sub.2 F).sub.2 CH.sub.3                    ##STR53##   CH.sub.2                                                                              CH(OH)    C(CH.sub.2 F).sub.2 CH.sub.3                    ##STR54##   CH.sub.2                                                                              CH(OH)    C(CH.sub.2 F).sub.2 CH.sub.3                   ______________________________________                                    

Further particularly preferred azoles of the formula (I) are mentionedin the preparative examples hereinbelow.

Some of the azoles of the formula (I) are known (see DE-A (GermanPublished Specification Nos.) 2,407,143 and 2,737,489).

Those azoles of the formula (I) in which R¹ represents an optionallysubstituted aryl radical, R² represents a tert.-butyl radical which ismonosubstituted or disubstituted by halogen, X represents methylene andY represents carbonyl or a group --CH(OH)--, are hitherto unknown.However, they can be prepared in a simple manner by reacting atriazolylmethyl-tert.-butyl ketone of the general formula ##STR55## inwhich

X³ represents a hydrogen or halogen atom and

Y³ represents a halogen atom,

with a compound of the general formula

    R.sup.20 --Z.sup.1                                         (X)

in which

R²⁰ represents an optionally substituted arylmethyl radical and

Z¹ represents an electron-attracting leaving group (such as halogen,p-methylphenylsulphonyloxy or sulphate),

in the usual manner in the presence of an inert organic solvent (such asdimethylsulphoxide) at a temperature between 0° C. and 100° C., and ifappropriate, reducing the azole of the formula ##STR56## formed thereby,in which

R¹, X³ and Y³ have the meanings given above, according to known methods,in the presence of an inert diluent, at a temperature between 0° C. and30° C. Complex hydrides (such as sodium borohydride, and lithiumalanate) and also aluminum isopropylate or hydrogen in the presence of acatalyst are examples of suitable reducing agents.

Preferred azoles of formula (II) are those in which,

R³ represents an optionally monosubstituted or disubstituted,straight-chain or branched alkyl radical having 1 to 4 carbon atoms,preferred suitable substituents being selected from halogen,alkylcarbonyloxy having 1 to 4 carbon atoms in the alkyl part,alkylsulphonyloxy having 1 to 4 carbon atoms, and phenylsulphonyloxywhich is optionally substituted by halogen or alkyl having 1 to 4 carbonatoms, or

R³ additionally represents a cycloalkyl radical having 5 to 7 carbonatoms, or an aryl radical which is optionally monosubstituted orpolysubstituted by identical or different substituents and which has 6to 10 carbon atoms (such as phenyl or naphthyl), preferred suitablesubstituents being selected from halogen, alkyl having 1 to 4 carbonatoms, phenyl, phenoxy, halogenophenyl and halogenophenoxy,

R⁴ represents a hydrogen atom or a straight-chain or branched alkylradical having 1 to 4 carbon atoms,

R⁵ represents a hydrogen atom, a straight-chain or branched alkylradical having 1 to 4 carbon atoms, a cycloalkyl radical having 5 to 7carbon atoms, a cycloalkenyl radical which has 5 to 7 carbon atoms andis optionally substituted by alkyl having 1 to 4 carbon atoms, analkenyl radical having 2 to 4 carbon atoms or an optionally substitutedaryl radical having 6 to 10 carbon atoms (such as phenyl or naphthyl),halogen and alkyl having 1 to 4 carbon atoms being preferred suitablesubstituents, or in addition

R⁴ and R⁵ together with the carbon atom to which they are bondedrepresent a cycloalkenyl radical which has 5 to 7 carbon atoms and whichis optionally substituted by alkyl having 1 to 4 carbon atoms, or acycloalkyl radical having 3 to 7 carbon atoms,

R⁶ represents a hydrogen atom or an alkyl radical having 1 to 4 carbonatoms,

X¹ represents a group --C(OR⁷)R⁸ --, or additionally represents a ketogroup if R³ represents an optionally substituted alkyl or cycloalkylradical,

R⁷ represents a hydrogen atom, a straight-chain or branched alkylradical having 1 to 4 carbon atoms, an aralkyl radical which isoptionally monosubstituted or polysubstituted by identical or differentsubstituents and which has 1 or 2 carbon atoms in the alkyl part and 6to 10 carbon atoms in the aryl part (such as benzyl or naphthylmethyl),preferred suitable substituents being selected from halogen, alkylhaving 1 to 4 carbon atoms, halogenoalkyl having up to 2 carbon atomsand up to 3 identical or different halogen atoms (fluorine and chlorinebeing preferred), and optionally halogen-substituted phenyl and phenoxy,or

R⁷ represents an acyl radical --CO--R²¹ or a carbamoyl radical--CO--NR²² R²³, wherein

R²¹ represents a straight-chain or branched alkyl radical having 1 to 4carbon atoms, a halogenoalkyl radical having 1 or 2 carbon atoms and 1to 5 identical or different halogen atoms (preferably fluorine andchlorine atoms) or an optionally substituted phenyl or benzyl radical,the preferred suitable substituents being selected from halogen andalkyl having 1 to 4 carbon atoms,

R²² represents a hydrogen atom or an alkyl radical having 1 to 4 carbonatoms,

R²³ represents an alkyl radical having 1 to 8 carbon atoms, ahalogenoalkyl radical having up to 4 carbon atoms and up to 5 identicalor different halogen atoms (such as, in particular, fluorine andchlorine atoms), an aryl radical which is optionally monosubstituted orpolysubstituted by identical or different substituents and which has 6to 10 carbon atoms (such as phenyl and naphthyl) the preferred suitablesubstituents being selected from halogen, alkyl having 1 to 4 carbonatoms, and halogenoalkyl having up to 2 carbon atoms and up to 5identical or different halogen atoms (such as, in particular, fluorineand chlorine atoms), or

R²³ also represents a halogenoalkylmercapto radical having 1 or 2 carbonatoms and up to 5 halogen atoms (such as, in particular, fluorine andchlorine atoms), and

R⁸ represents a hydrogen atom, an alkyl radical having 1 to 4 carbonatoms or an aralkyl radical which has 1 or 2 carbon atoms in the alkylpart and 6 to 10 carbon atoms in the aryl part and which is optionallysubstituted by halogen or alkyl having 1 to 4 carbon atoms (such as,preferably, benzyl).

Those compounds of the formula (II) are very particularly preferred, inwhich

R³ represents a tert.-butyl, isopropyl, chloro-tert.-butyl,bromo-tert.-butyl, fluoro-tert.-butyl, acetoxy-tert.-butyl,methylsulphonyloxy-tert.-butyl, p-toluenesulphonyloxy-tert.-butyl,1,3-dichloro-2-methylprop-2-yl, 1,3-dibromo-2-methylprop-2-yl,1,3-difluoro-2-methylprop-2-yl, 1-chloro-3-bromo-2-methylprop-2-yl,1,3-diacetoxy-2-methylprop-2-yl, cyclohexyl, phenyl, chlorophenyl,bromophenyl, dichlorophenyl, fluorophenyl, methylphenyl, dimethylphenyl,chloromethylphenyl, biphenyl, phenoxyphenyl, chlorophenylphenyl orchlorophenoxyphenyl radical;

R⁴ represents a hydrogen atom or a methyl, ethyl, propyl or butylradical;

R⁵ represents a hydrogen atom or a methyl, ethyl, isopropyl, cyclohexyl,cyclohexenyl, methylcyclohexenyl, allyl, methacryl, phenyl,chlorophenyl, dichlorophenyl or methylphenyl radical; or

R⁴ and R⁵ together with the carbon atom to which they are bondedrepresent cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cyclohexenyl, or methylcyclohexenyl;

R⁶ represents a hydrogen atom or a methyl, ethyl or n-propyl radical;

X¹ represents a group --C(OR⁷)R⁸ -- or also represents a keto group ifR³, as optionally substituted alkyl or cycloalkyl, has the meaningsalready given immediately above;

R⁷ represents a hydrogen atom or a methyl, ethyl, n-propyl, isopropyl orisobutyl radical, a naphthyl radical which is optionally substituted bychlorine, a benzyl radical which is optionally monosubstituted orpolysubstituted, the substituents being identical or different, by asubstituent selected from chlorine, fluorine, methyl, phenyl,chlorophenyl, phenoxy or chlorophenoxy, an acyl radical of the generalformula --COR²¹ or a carbamoyl radical of the general formula --CO--NR²²R²³ ; wherein

R²¹ represents a methyl, ethyl, isopropyl, isobutyl, chloromethyl ordichloromethyl radical or an optionally monosubstituted orpolysubstituted phenyl or benzyl radical having chlorine, bromine ormethyl as the substituents;

R²² represents a hydrogen atom or a methyl or ethyl radical, and

R²³ represents a methyl, ethyl, chloroethyl, phenyl, chlorophenyl,trifluoromethylmercapto, chlorodifluoromethylmercapto,dichlorofluoro-methylmercapto or trichloromethyl-mercapto radical, and

R⁸ represents a hydrogen atom or a methyl, ethyl, isopropyl, benzyl,chlorobenzyl, or dichlorobenzyl radical;

The compounds listed in the following table may be individuallymentioned as examples of azoles of the formula (II).

    ______________________________________                                         ##STR57##                                                                    R.sup.3               R.sup.4 R.sup.5                                         ______________________________________                                        C(CH.sub.3).sub.3     C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                 C(CH.sub.3).sub.3     C.sub.2 H.sub.5                                                                       CH.sub.3                                        C(CH.sub.3).sub.3     CH.sub.3                                                                              CH.sub.3                                        C(CH.sub.3).sub.3     CH.sub.3                                                                               ##STR58##                                      C(CH.sub.3).sub.3     CH.sub.3                                                                               ##STR59##                                      C(CH.sub.3).sub.3     Cyclopropyl                                             C(CH.sub.3).sub.3     Cyclobutyl                                              C(CH.sub.3).sub.3     Cyclopentyl                                             C(CH.sub.3).sub.3     Cycloheptyl                                             C(CH.sub.3).sub.3     Norborn-3-en-2-yl                                        ##STR60##            Cyclohexane                                              ##STR61##            Cyclohexene                                              ##STR62##            Methylcyclohexene                                        ##STR63##            CH.sub.3                                                                              CH.sub.3                                         ##STR64##            Cyclohexane                                              ##STR65##            Cyclohexene                                              ##STR66##            Methylcyclohexene                                        ##STR67##            Methylcyclohexene                                        ##STR68##            CH.sub.3                                                                              CH.sub.3                                         ##STR69##            Cyclohexane                                              ##STR70##            Cyclohexene                                              ##STR71##            Methylcyclohexene                                        ##STR72##            CH.sub.3                                                                              CH.sub.3                                         ##STR73##            Cyclohexane                                              ##STR74##            Cyclohexene                                              ##STR75##            Methylcyclohexene                                        ##STR76##            CH.sub.3                                                                              CH.sub.3                                         ##STR77##            Cyclohexane                                              ##STR78##            Cyclohexene                                              ##STR79##            Methylcyclohexene                                        ##STR80##            CH.sub.3                                                                              CH.sub.3                                         ##STR81##            Cyclohexane                                              ##STR82##            Cyclohexene                                              ##STR83##            Methylcyclohexene                                        ##STR84##            CH.sub.3                                                                              CH.sub.3                                         ##STR85##            Cyclohexane                                              ##STR86##            Cyclohexene                                              ##STR87##            Methylcyclohexene                                        ##STR88##            CH.sub.3                                                                              CH.sub.3                                         ##STR89##            Cyclohexane                                              ##STR90##            Cyclohexene                                              ##STR91##            Methylcyclohexene                                        ##STR92##            CH.sub.3                                                                              CH.sub.3                                         ##STR93##            Cyclohexane                                              ##STR94##            Cyclohexene                                              ##STR95##            Methylcyclohexene                                        ##STR96##            CH.sub.3                                                                              CH.sub.3                                        ______________________________________                                    

    __________________________________________________________________________     ##STR97##                           (IIb)                                    R.sup.3             R.sup.4                                                                           R.sup.5                                                                             R.sup.8                                         __________________________________________________________________________    C(CH.sub.3).sub.3   C.sub.2 H.sub.5                                                                   CH.sub.3                                                                            H                                               C(CH.sub.3).sub.3   CH.sub.3                                                                          CH.sub.3                                                                            H                                               C(CH.sub.3).sub.3   CH.sub.3                                                                           ##STR98##                                                                          H                                               C(CH.sub.3).sub.3   CH.sub.3                                                                           ##STR99##                                                                          H                                               C(CH.sub.3).sub.3   Cyclopropyl                                                                             H                                               C(CH.sub.3).sub.3   Cyclobutyl                                                                              H                                               C(CH.sub.3).sub.3   Cyclopentyl                                                                             H                                               C(CH.sub.3).sub.3   Cycloheptyl                                                                             H                                               C(CH.sub.3).sub.3   CH.sub.3                                                                          CH.sub.3                                                                            CH.sub.3                                        C(CH.sub.3).sub.3   Cyclohexane                                                                             CH.sub.3                                        C(CH.sub.3).sub.3   Cyclohexene                                                                             CH.sub.3                                        C(CH.sub.3).sub.3   Methylcyclohexene                                                                       CH.sub.3                                        C(CH.sub.3).sub.3   CH.sub.3                                                                          CH.sub.3                                                                             ##STR100##                                     C(CH.sub.3).sub.3   Cyclohexane                                                                              ##STR101##                                     C(CH.sub.3).sub.3   Cyclohexene                                                                              ##STR102##                                     C(CH.sub.3).sub.3   Methylcyclohexene                                                                        ##STR103##                                      ##STR104##                                                                                       CH.sub.3                                                                          CH.sub.3                                                                            H                                                ##STR105##                                                                                       Cyclohexane                                                                             H                                                ##STR106##         Cyclohexene                                                                             H                                                ##STR107##         Methylcyclohexene                                                                       H                                                ##STR108##         CH.sub.3                                                                          CH.sub.3                                                                            H                                                ##STR109##         Cyclohexane                                                                             H                                                ##STR110##         Cyclohexene                                                                             H                                                ##STR111##         Methylcyclohexene                                                                       H                                                ##STR112##         CH.sub.3                                                                          CH.sub.3                                                                            H                                                ##STR113##         Cyclohexane                                                                             H                                                ##STR114##         Cyclohexene                                                                             H                                                ##STR115##         Methylcyclohexene                                                                       H                                                ##STR116##         CH.sub.3                                                                          CH.sub.3                                                                            H                                                ##STR117##         Cyclohexane                                                                             H                                                ##STR118##         Cyclohexene                                                                             H                                                ##STR119##         Methylcyclohexene                                                                       H                                                ##STR120##         CH.sub.3                                                                          CH.sub.3                                                                            H                                                ##STR121##         Cyclohexane                                                                             H                                                ##STR122##         Cyclohexene                                                                             H                                                ##STR123##         Methylcyclohexene                                                                       H                                                ##STR124##         CH.sub.3                                                                          CH.sub.3                                                                            H                                                ##STR125##         Cyclohexane                                                                             H                                                ##STR126##         Cyclohexene                                                                             H                                                ##STR127##         Methylcyclohexene                                                                       H                                                ##STR128##         CH.sub.3                                                                          CH.sub.3                                                                            H                                                ##STR129##         Cyclohexane                                                                             H                                                ##STR130##         Cyclohexene                                                                             H                                                ##STR131##         Methylcyclohexene                                                                       H                                                ##STR132##         CH.sub.3                                                                          CH.sub.3                                                                            H                                                ##STR133##         Cyclohexane                                                                             H                                                ##STR134##         Cyclohexene                                                                             H                                                ##STR135##         Methylcyclohexene                                                                       H                                                ##STR136##         CH.sub.3                                                                          CH.sub.3                                                                            H                                                ##STR137##         Cyclohexane                                                                             H                                                ##STR138##         Cyclohexene                                                                             H                                                ##STR139##         Methylcyclohexene                                                                       H                                                ##STR140##         CH.sub.3                                                                          CH.sub.3                                                                            H                                                ##STR141##         Cyclohexane                                                                             H                                                ##STR142##         Cyclohexene                                                                             H                                                ##STR143##         Methylcyclohexene                                                                       H                                                ##STR144##         CH.sub.3                                                                          CH.sub.3                                                                            H                                                ##STR145##         Cyclohexane                                                                             H                                                ##STR146##         Cyclohexene                                                                             H                                                ##STR147##         Methylcyclohexene                                                                       H                                               __________________________________________________________________________

    ______________________________________                                         ##STR148##                   (IIc)                                           R.sup.3   R.sup.4  R.sup.5  R.sup.7     R.sup.8                               ______________________________________                                        C(CH.sub.3).sub.3                                                                       CH.sub.3 CH.sub.3 C.sub.2 H.sub.5                                                                           H                                     C(CH.sub.3).sub.3                                                                       Cyclohexane   C.sub.2 H.sub.5                                                                             H                                       C(CH.sub.3).sub.3                                                                       Cyclohexene   C.sub.2 H.sub.5                                                                             H                                       C(CH.sub.3).sub.4                                                                       Methylcyclohexene                                                                           C.sub.2 H.sub.5                                                                             H                                        ##STR149##                                                                             CH.sub.3 CH.sub.3 C.sub.2 H.sub.5                                                                           CH.sub.3                               ##STR150##                                                                             Cyclohexane   C.sub.2 H.sub.5                                                                             CH.sub.3                                 ##STR151##                                                                             Cyclohexene   C.sub.2 H.sub.5                                                                             CH.sub.3                                 ##STR152##                                                                             Methylcyclohexene                                                                           C.sub.2 H.sub.5                                                                             CH.sub.3                                 ##STR153##                                                                             CH.sub.3 CH.sub.3 C.sub.2 H.sub.5                                                                           H                                      ##STR154##                                                                             Cyclohexane   C.sub.2 H.sub.5                                                                             H                                        ##STR155##                                                                             Cyclohexene   C.sub.2 H.sub.5                                                                             H                                        ##STR156##                                                                             Methylcyclohexene                                                                           C.sub.2 H.sub.5                                                                             H                                        ##STR157##                                                                             CH.sub.3 CH.sub.3 C.sub.2 H.sub.5                                                                           H                                      ##STR158##                                                                             Cyclohexane   C.sub.2 H.sub.5                                                                             H                                        ##STR159##                                                                             Cyclohexene   C.sub. 2 H.sub.5                                                                            H                                        ##STR160##                                                                             Methylcyclohexene                                                                           C.sub.2 H.sub.5                                                                             H                                       C(CH.sub.3).sub.3                                                                       CH.sub.3 CH.sub.3                                                                                ##STR161## H                                     C(CH.sub.3).sub.3                                                                       Cyclohexane                                                                                  ##STR162##   H                                       C(CH.sub.3).sub.3                                                                       Cyclohexene                                                                                  ##STR163##   H                                       C(CH.sub.3).sub.3                                                                       Methylcyclohexene                                                                            ##STR164##   H                                        ##STR165##                                                                             CH.sub.3 CH.sub.3                                                                                ##STR166## H                                      ##STR167##                                                                             Cyclohexane                                                                                  ##STR168##   H                                        ##STR169##                                                                             Cyclohexene                                                                                  ##STR170##   H                                        ##STR171##                                                                             Methylcyclohexene                                                                            ##STR172##   H                                        ##STR173##                                                                             CH.sub.3 CH.sub.3                                                                                ##STR174## H                                      ##STR175##                                                                             Cyclohexane                                                                                  ##STR176##   H                                        ##STR177##                                                                             Cyclohexane                                                                                  ##STR178##   H                                        ##STR179##                                                                             Methylcyclohexene                                                                            ##STR180##   H                                        ##STR181##                                                                             CH.sub.3 CH.sub.3                                                                                ##STR182## H                                      ##STR183##                                                                             Cyclohexane                                                                                  ##STR184##   H                                        ##STR185##                                                                             Cyclohexene                                                                                  ##STR186##   H                                        ##STR187##                                                                             Methylcyclohexene                                                                            ##STR188##   H                                        ##STR189##                                                                             CH.sub.3 CH.sub.3 COCH.sub.3  H                                      ##STR190##                                                                             Cyclohexane   COCH.sub.3    H                                        ##STR191##                                                                             Cyclohexene   COCH.sub.3    H                                        ##STR192##                                                                             Methylcyclohexene                                                                           COCH.sub.3    H                                        ##STR193##                                                                             CH.sub.3 CH.sub.3 COCH.sub.3  H                                      ##STR194##                                                                             Cyclohexane   COCH.sub.3    H                                        ##STR195##                                                                             Cyclohexene   COCH.sub.3    H                                        ##STR196##                                                                             Methylcyclohexene                                                                           COCH.sub.3    H                                        ##STR197##                                                                             CH.sub.3 CH.sub.3 COCH.sub.3  H                                      ##STR198##                                                                             Cyclohexane   COCH.sub.3    H                                        ##STR199##                                                                             Cyclohexene   COCH.sub.3    H                                        ##STR200##                                                                             Methylcyclohexene                                                                           COCH.sub.3    H                                        ##STR201##                                                                             CH.sub.3 CH.sub.3 CONHCH.sub.3                                                                              H                                      ##STR202##                                                                             Cyclohexane   CONHCH.sub.3  H                                        ##STR203##                                                                             Cyclohexene   CONHCH.sub.3  H                                        ##STR204##                                                                             Methylcyclohexene                                                                           CONHCH.sub.3  H                                        ##STR205##                                                                             CH.sub.3 CH.sub.3 CONHCH.sub.3                                                                              H                                      ##STR206##                                                                             Cyclohexane   CONHCH.sub.3  H                                        ##STR207##                                                                             Cyclohexene   CONHCH.sub.3  H                                        ##STR208##                                                                             Methylcyclohexene                                                                           CONHCH.sub.3  H                                        ##STR209##                                                                             CH.sub.3 CH.sub.3 CONHCH.sub.3                                                                              H                                      ##STR210##                                                                             Cyclohexane   CONHCH.sub.3  H                                        ##STR211##                                                                             Cyclohexene   CONHCH.sub.3  H                                        ##STR212##                                                                             Methylcyclohexene                                                                           CONHCH.sub.3  H                                        ##STR213##                                                                             CH.sub.3 CH.sub.3                                                                                ##STR214## H                                      ##STR215##                                                                             Cyclohexane                                                                                  ##STR216##   H                                        ##STR217##                                                                             Cyclohexene                                                                                  ##STR218##   H                                        ##STR219##                                                                             Methylcyclohexene                                                                            ##STR220##   H                                        ##STR221##                                                                             CH.sub.3 CH.sub.3                                                                                ##STR222## H                                      ##STR223##                                                                             Cyclohexane                                                                                  ##STR224##   H                                        ##STR225##                                                                             Cyclohexene                                                                                  ##STR226##   H                                        ##STR227##                                                                             Methylcyclohexene                                                                            ##STR228##   H                                        ##STR229##                                                                             CH.sub.3 CH.sub.3                                                                                ##STR230## H                                      ##STR231##                                                                             Cyclohexane                                                                                  ##STR232##   H                                        ##STR233##                                                                             Cyclohexene                                                                                  ##STR234##   H                                        ##STR235##                                                                             Methylcyclohexene                                                                            ##STR236##   H                                        ##STR237##                                                                             CH.sub.3 CH.sub.3                                                                                ##STR238## H                                      ##STR239##                                                                             Cyclohexane                                                                                  ##STR240##   H                                        ##STR241##                                                                             Cyclohexene                                                                                  ##STR242##   H                                        ##STR243##                                                                             Methylcyclohexene                                                                            ##STR244##   H                                        ##STR245##                                                                             CH.sub.3 CH.sub.3                                                                                ##STR246## H                                      ##STR247##                                                                             Cyclohexane                                                                                  ##STR248##   H                                        ##STR249##                                                                             Cyclohexene                                                                                  ##STR250##   H                                        ##STR251##                                                                             Methylcyclohexene                                                                            ##STR252##   H                                        ##STR253##                                                                             CH.sub.3 CH.sub.3                                                                                ##STR254## H                                      ##STR255##                                                                             Cyclohexane                                                                                  ##STR256##   H                                        ##STR257##                                                                             Cyclohexene                                                                                  ##STR258##   H                                        ##STR259##                                                                             Methylcyclohexene                                                                            ##STR260##   H                                        ##STR261##                                                                             CH.sub.3 CH.sub.3 COCHCl.sub.2                                                                              H                                      ##STR262##                                                                             Cyclohexane   COCHCl.sub.2  H                                        ##STR263##                                                                             Cyclohexene   COCHCl.sub.2  H                                        ##STR264##                                                                             Methylcyclohexene                                                                           COCHCl.sub.2  H                                        ##STR265##                                                                             CH.sub.3 CH.sub.3 COCHCl.sub.2                                                                              H                                      ##STR266##                                                                             Cyclohexane   COCHCl.sub.2  H                                        ##STR267##                                                                             Cyclohexene   COCHCl.sub.2  H                                        ##STR268##                                                                             Methylcyclohexene                                                                           COCHCl.sub.2  H                                        ##STR269##                                                                             CH.sub.3 CH.sub.3 COCHCl.sub.2                                                                              H                                      ##STR270##                                                                             Cyclohexane   COCHCl.sub.2  H                                        ##STR271##                                                                             Cyclohexene   CO CHCl.sub.2 H                                        ##STR272##                                                                             Methylcyclohexene                                                                           COCHCl.sub.2  H                                       C(CH.sub.3).sub.3                                                                       CH.sub.3 CH.sub.3 COCH.sub.3  H                                     C(CH.sub.3).sub.3                                                                       Cyclohexane   COCH.sub.3    H                                       C(CH.sub.3).sub.3                                                                       Cyclohexene   COCH.sub.3    H                                       C(CH.sub.3).sub.3                                                                       Methylcyclohexene                                                                           COCH.sub.3    H                                       C(CH.sub.3).sub.3                                                                       CH.sub.3 CH.sub.3 CONHCH.sub.3                                                                              H                                     C(CH.sub.3).sub.3                                                                       Cyclohexane   CONHCH.sub.3  H                                       C(CH.sub.3).sub.3                                                                       Cyclohexene   CONHCH.sub.3  H                                       C(CH.sub.3).sub.3                                                                       Methylcyclohexene                                                                           CONHCH.sub.3  H                                       C(CH.sub.3).sub.3                                                                       CH.sub.3 CH.sub.3                                                                                ##STR273## H                                     C(CH.sub.3).sub.3                                                                       Cyclohexane                                                                                  ##STR274##   H                                       C(CH.sub.3).sub.3                                                                       Cyclohexene                                                                                  ##STR275##   H                                       C(CH.sub.3).sub.3                                                                       Methylcyclohexene                                                                            ##STR276##   H                                       C(CH.sub.3).sub.3                                                                       CH.sub.3 CH.sub.3                                                                                ##STR277## H                                     C(CH.sub.3).sub.3                                                                       Cyclohexane                                                                                  ##STR278##   H                                       C(CH.sub.3).sub.3                                                                       Cyclohexane                                                                                  ##STR279##   H                                       C(CH.sub.3).sub.3                                                                       Methylcyclohexene                                                                            ##STR280##   H                                       C(CH.sub.3).sub.3                                                                       CH.sub.3 CH.sub.3 COCHCl.sub.2                                                                              H                                     C(CH.sub.3).sub.3                                                                       Cyclohexane   COCHCl.sub.2  H                                       C(CH.sub.3).sub.3                                                                       Cyclohexene   COCHCl.sub.2  H                                       C(CH.sub.3).sub.3                                                                       Methylcyclohexene                                                                           COCHCl.sub.2  H                                       ______________________________________                                    

Further particularly preferred azoles of the formula (II) are mentionedin the Preparative Examples.

The azoles of the formula (II) are already known (see U.S. applicationSer. No. 152,949 filed May 23, 1980, now pending and DE-A (GermanPublished Specification) 2,645,617).

The compounds of the formula (II) can be present in two geometric isomerforms, according to the arrangement of the groups which are bonded tothe double bond. If X¹ represents the group --C(OR⁷)R⁸ --, an asymmetriccarbon atom is present, so that the compounds of the formula (II) mayadditionally be present in two optical isomer forms. The presentinvention relates to compositions comprising the individual isomers aswell as compositions comprising the isomer mixtures.

Preferred azoles of formula (III) are those in which,

R⁹ represents a phenyl radical which is optionally monosubstituted,disubstituted or trisubstituted, the substituents being identical ordifferent, and being selected from fluorine, chlorine, bromine, phenyl,phenoxy, nitro, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4carbon atoms, cycloalkyl having 3 to 7 carbon atoms, halogenoalkylhaving 1 to 4 carbon atoms and 1 to 5 halogen atoms (particularlyfluorine, chlorine and bromine atoms) and cyano,

R¹⁰ represents a straight-chain or branched alkyl radical having 1 to 6carbon atoms, a halogenoalkyl radical having 1 to 6 carbon atoms and 1to 5 halogen atoms (fluorine, chlorine and bromine being preferred), aphenyl radical which is optionally monosubstituted, disubstituted ortrisubstituted, the substituents being identical or different, and beingselected from fluorine, chlorine, bromine, phenyl, phenoxy, nitro, alkylhaving 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms,cycloalkyl having 3 to 7 carbon atoms, halogenoalkyl having 1 to 4carbon atoms and 1 to 5 halogen atoms (particularly fluorine, chlorineand bromine atoms) and cyano, and

Y¹ represents a carbonyl group or a group --CH(OH)--.

The compounds listed in the following table may be individuallymentioned as examples of azoles of the formula (III):

    ______________________________________                                         ##STR281##                   (III)                                           R.sup.9          Y.sup.1   R.sup.10                                           ______________________________________                                         ##STR282##      CH(OH)    tert.-C.sub.4 H.sub.9                               ##STR283##      CH(OH)    tert.-C.sub.4 H.sub.9                               ##STR284##      CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 Cl                       ##STR285##      CO        tert.-C.sub.4 H.sub.9                               ##STR286##      CO        tert.-C.sub.4 H.sub.9                               ##STR287##      CO        C(CH.sub.3).sub.2 CH.sub.2 Cl                       ##STR288##      CO        C(CH.sub.3).sub.2 CH.sub.2 Cl                       ##STR289##      CO                                                                                       ##STR290##                                         ##STR291##      CO                                                                                       ##STR292##                                         ##STR293##      CO                                                                                       ##STR294##                                         ##STR295##      CO                                                                                       ##STR296##                                         ##STR297##      CO                                                                                       ##STR298##                                         ##STR299##      CO                                                                                       ##STR300##                                         ##STR301##      CO        CH.sub.3                                            ##STR302##      CO        C.sub.2 H.sub.5                                     ##STR303##      CO        C.sub.3 H.sub.7 -n                                  ##STR304##      CO        C.sub.3 H.sub.7 -iso                                ##STR305##      CH(OH)    tert.-C.sub.4 H.sub.9                               ##STR306##      CH(OH)    tert.-C.sub.4 H.sub.9                               ##STR307##      CH(OH)    tert.-C.sub.4 H.sub.9                               ##STR308##      CO        C(CH.sub.2 Cl).sub.2 CH.sub.3                       ##STR309##      CH(OH)    C(CH.sub.2 Cl).sub.2 CH.sub.3                       ##STR310##      CO        C(CH.sub.2 Cl).sub.2 CH.sub.3                       ##STR311##      CH(OH)    C(CH.sub.2 Cl).sub.2 CH.sub.3                       ##STR312##      CO        C(CH.sub.2 Cl).sub.2 CH.sub.3                       ##STR313##      CH(OH)    C(CH.sub.2 Cl).sub.2 CH.sub.3                       ##STR314##      CO        C(CH.sub.2 Cl).sub.2 CH.sub.3                       ##STR315##      CH(OH)    C(CH.sub.2 Cl).sub.2 CH.sub.3                       ##STR316##      CO        C(CH.sub.2 F).sub.2 CH.sub.3                        ##STR317##      CH(OH)    C(CH.sub.2 F).sub.2 CH.sub.3                        ##STR318##      CO        C(CH.sub.2 F).sub.2 CH.sub.3                        ##STR319##      CH(OH)    C(CH.sub.2 F).sub.2 CH.sub.3                        ##STR320##      CO        C(CH.sub.2 F).sub.2 CH.sub.3                        ##STR321##      CH(OH)    C(CH.sub.2 F).sub.2 CH.sub.3                        ##STR322##      CO        C(CH.sub.2 F).sub.2 CH.sub.3                        ##STR323##      CH(OH)    C(CH.sub.2 F).sub.2 CH.sub.3                        ##STR324##      CO        C(CH.sub.3).sub.2 CH.sub.2 Cl                       ##STR325##      CO        C(CH.sub.3).sub.2 CH.sub.2 Cl                       ##STR326##      CO         C(CH.sub.3).sub.2 CH.sub.2 Cl                      ##STR327##      CO        C(CH.sub.3).sub.2 CH.sub.2 Cl                       ##STR328##      CO        C(CH.sub.3).sub.2 CH.sub.2 Cl                       ##STR329##      CO        C(CH.sub.3).sub.2 CH.sub.2 Cl                       ##STR330##      CO        C(CH.sub.3).sub.2 CH.sub.2 Cl                       ##STR331##      CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 Cl                       ##STR332##      CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 Cl                       ##STR333##      CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 Cl                       ##STR334##      CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 Cl                       ##STR335##      CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 Cl                       ##STR336##      CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 Cl                       ##STR337##      CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 Cl                       ##STR338##      CO        C(CH.sub.3).sub.2 CH.sub.2 F                        ##STR339##      CO        C(CH.sub.3).sub.2 CH.sub.2 F                        ##STR340##      CO        C(CH.sub.3).sub.2 CH.sub.2 F                        ##STR341##      CO        C(CH.sub.3).sub.2 CH.sub.2 F                        ##STR342##      CO        C(CH.sub.3).sub.2 CH.sub.2 F                        ##STR343##      CO        C(CH.sub.3).sub.2 CH.sub. 2 F                       ##STR344##      CO        C(CH.sub.3).sub.2 CH.sub.2 F                        ##STR345##      CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 F                        ##STR346##      CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 F                        ##STR347##      CH(OH)    C(CH.sub.2).sub.2 CH.sub.2 F                        ##STR348##      CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 F                        ##STR349##      CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 F                        ##STR350##      CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 F                        ##STR351##      CH(OH)    C(CH.sub.3).sub.2 CH.sub.2 F                       ______________________________________                                    

Further particularly preferred azoles of the formula (III) are mentionedin the preparative examples hereinbelow.

Some of the azoles of the formula (III) are known (see DE-A (GermanPublished Specification Nos.) 2,645,617, 2,838,847, JP-A (JapanesePublished Specification) 53,130,661 and U.S. application Ser. No.144,110, filed Apr. 28, 1980, now pending.

The azoles of the formula (III) can be present in two geometric isomerforms, according to the arrangement of the groups which are bonded tothe double bond. If Y¹ represents the group --CH(OH)--, an asymmetriccarbon atom is present, so that the compounds of the formula (III) canalso be present in this case in two optical isomer forms. The presentinvention relates to compositions comprising the individual isomers aswell as compositions comprising the isomer mixtures.

Those azoles of the formula (III) in which R⁹ represents an optionallysubstituted aryl radical, R¹⁰ represents a tert.-butyl radical which ismonosubstituted or disubstituted by halogen, and Y¹ represents acarbonyl group or a group --CH(OH)--, are hitherto unknown. However,they can be prepared in a simple manner by reacting atriazolylmethyl-tert.-butyl ketone of the general formula ##STR352## inwhich

X³ and Y³ have the meanings given above, with an aldehyde of the generalformula

    R.sup.9 --CH═O                                         (XI)

in which

R⁹ has the meaning given above, in the presence of an inert organicsolvent and in the presence of a catalyst (such as a mixture ofpiperidine and glacial acetic acid) at a temperature between 20° C. and160° C., and, if appropriate, reducing the azole of the general formula##STR353## formed thereby, in which,

R⁹, X³ and Y³ have the meanings given above, according to known methods,in the presence of an inert diluent at a temperature between 0° C. and30° C. Complex hydrides (such as sodium borohydride and lithium alanate)and also aluminum isopropylate or hydrogen in the presence of a catalystare examples of suitable reducing agents.

Preferred azoles of formula (IV) are those in which,

R¹¹ and R¹² are identical or different and represent a cycloalkylradical which is optionally substituted by methyl and which has 5 or 6carbon atoms, a straight-chain or branched alkyl radical having 1 to 4carbon atoms, a halogenoalkyl radical having 1 to 4 carbon atoms and 1to 5 halogen atoms (such as fluorine or chlorine) or a phenyl radicalwhich is optionally substituted by substituent(s) selected fromfluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms, alkoxyhaving 1 to 4 carbon atoms, phenyl and nitro.

The azoles of the formula (IV) are known (see EP-A (European PublishedPatent Application) 0,005,600).

Preferred azoles of formula (V), are those in which,

R¹³ represents a straight-chain or branched alkyl radical having 1 to 4carbon atoms, a cycloalkyl radical which has 3 to 7 carbon atoms andwhich is optionally substituted by alkyl having 1 or 2 carbon atoms, ora phenyl radical which is optionally monosubstituted or polysubstitutedby identical or different substituents, preferred suitable substituentsbeing selected from halogen, alkyl having 1 to 4 carbon atoms andhalogenoalkyl having 1 to 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms (such as, in particular, fluorine and chlorineatoms),

Z represents a halogen atom, a straight-chain or branched alkyl radicalhaving 1 to 4 carbon atoms, a cycloalkyl radical having 5 to 7 carbonatoms, an alkoxy and alkylthio radical, each having 1 to 4 carbon atoms,a halogenoalkyl, halogenoalkoxy or halogenoalkylthio radical each having1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms(such as, in particular, fluorine and chlorine atoms), or an optionallyhalogen-and/or C₁₋₄ -alkyl-substituted phenyl, phenoxy, phenylalkyl orphenylalkoxy radical having 1 or 2 carbon atoms in the alkyl or alkoxypart, and

X², Y² and m have the meanings given above.

Particularly preferred azoles of formula (VI) are those in which

R¹³ represents a tert.-butyl, isopropyl or methyl radical, acyclopropyl, cyclopentyl or cyclohexyl radical, which is optionallysubstituted by methyl in each case, or a phenyl radical which isoptionally monosubstituted or disubstituted, the substituents beingidentical or different and being selected from fluorine, chlorine,methyl and trifluoromethyl;

Z represents a fluorine, chlorine or bromine atom, a methyl,tert.-butyl, cyclohexyl, methoxy, methylthio, trifluoromethyl,trifluoromethoxy or trifluoromethylthio radical or a phenyl, phenoxy,benzyl or benzyloxy radical which is in each case optionallymonosubstituted or disubstituted, the substituents being identical ordifferent and being selected from fluorine, chlorine and methyl, and

X², Y² and m have the meaning given above.

The compounds listed in the following table may be individuallymentioned as examples of azole of the formula (V): ##STR354##

    __________________________________________________________________________    Z.sub.m        Y.sup.2  R.sup.13 X.sup.2                                      __________________________________________________________________________                   OCH.sub.2                                                                              C(CH.sub.3).sub.3                                                                      N(CH)                                         ##STR355##    "        "        "                                             ##STR356##    "        "        "                                             ##STR357##    "        "        "                                             ##STR358##    "        "        "                                             ##STR359##    "        "        "                                             ##STR360##    "        "        "                                             ##STR361##    "        "        "                                            3,4-Cl.sub.2   "        "        "                                            4-CF.sub.3     "        "        "                                            4-OCF.sub.3    "        "        "                                            4-SCF.sub.3    "        "        "                                            4-SCH.sub.3    "        "        "                                            4-C(CH.sub.3).sub.3                                                                          "        "        "                                             ##STR362##    OCH.sub.2                                                                               ##STR363##                                                                            N(CH)                                         ##STR364##    "        "        "                                             ##STR365##    "        "        "                                             ##STR366##    "        "        "                                             ##STR367##    "        "        "                                             ##STR368##    "        "        "                                             ##STR369##    "        "        "                                             ##STR370##    "        "        "                                            3,4-Cl.sub.2   "        "        "                                            4-CF.sub.3     "        "        "                                            4-OCF.sub.     "        "        "                                            4-SCF.sub.3    "        "        "                                            4-SCH.sub.3    "        "        "                                            4-C(CH.sub.3).sub.3                                                                          "        "        "                                             ##STR371##    OCH.sub.2                                                                              CH(CH.sub.3).sub.2                                                                     N(CH)                                         ##STR372##    "        "        "                                             ##STR373##    "        "        "                                             ##STR374##    "        "        "                                             ##STR375##    "        "        "                                             ##STR376##    "        "        "                                             ##STR377##    "        "        "                                             ##STR378##    "        "        "                                            3,4-Cl.sub.2   "        "        "                                            4-CF.sub.3     "        "        "                                            4-OCF.sub.3    "        "        "                                            4-SCF.sub.3    "        "        "                                            4-SCH.sub.3    "        "        "                                            4-C(CH.sub.3).sub.3                                                                          "        "        "                                             ##STR379##    OCH.sub.2                                                                               ##STR380##                                                                            N(CH)                                         ##STR381##    "        "        "                                             ##STR382##    "        "        "                                             ##STR383##    "        "        "                                             ##STR384##    "        "        "                                             ##STR385##    "        "        "                                             ##STR386##    "        "        "                                             ##STR387##    "        "        "                                            3,4-Cl.sub.2   "        "        "                                            4-CF.sub.3     "        "        "                                            4-OCF.sub.3    "        "        "                                            4-SCF.sub.3    "        "        "                                            4-SCH.sub.3    "        "        "                                            4-C(CH.sub.3).sub.3                                                                          "        "        "                                             ##STR388##    OCH.sub.2                                                                               ##STR389##                                                                            N(CH)                                         ##STR390##    "        "        "                                             ##STR391##    "        "        "                                             ##STR392##    "        "        "                                             ##STR393##    "        "        "                                             ##STR394##    "        "        "                                             ##STR395##    "        "        "                                             ##STR396##    "        "        "                                            3,4-Cl.sub.2   "        "        "                                            4-CF.sub.3     "        "        "                                            4-OCF.sub.3    "        "        "                                            4-SCF.sub.3    "        "        "                                            4-SCH.sub.3    "        "        "                                            4-C(CH.sub.3).sub.3                                                                          "        "        "                                             ##STR397##    CH.sub.2CH.sub.2                                                                       C(CH.sub.3).sub.3                                                                      N(CH)                                         ##STR398##    "        "        "                                             ##STR399##    "        "        "                                             ##STR400##    "        "        "                                             ##STR401##    "        "        "                                             ##STR402##    "        "        "                                             ##STR403##    "        "        "                                             ##STR404##    "        "        "                                            3,4-Cl.sub.2   "        "        "                                            4-CF.sub.3     "        "        "                                            4-OCF.sub.3    "        "        "                                            4-SCF.sub.3    "        "        "                                            4-SCH.sub.3    "        "        "                                            4-C(CH.sub.3).sub.3                                                                          "        "        "                                             ##STR405##    CH.sub.2CH.sub.2                                                                        ##STR406##                                                                            N(CH)                                         ##STR407##    "        "        "                                             ##STR408##    "        "        "                                             ##STR409##    "        "        "                                             ##STR410##    "        "        "                                             ##STR411##    "        "        "                                             ##STR412##    "        "        "                                             ##STR413##    "        "        "                                            3,4-Cl.sub.2   "        "        "                                            4-CF.sub.3     "        "        "                                            4-OCF.sub.3    "        "        "                                            4-SCF.sub.3    "        "        "                                            4-SCH.sub.3    "        "        "                                            4-C(CH.sub.3).sub.3                                                                          "        "        "                                             ##STR414##    CH.sub.2CH.sub.2                                                                       CH(CH.sub.3).sub.2                                                                     N(CH)                                         ##STR415##    "        "        "                                             ##STR416##    "        "        "                                             ##STR417##    "        "        "                                             ##STR418##    "        "        "                                             ##STR419##    "        "        "                                             ##STR420##    "        "        "                                             ##STR421##    "        "        "                                            3,4-Cl.sub.2   "        "        "                                            4-CF.sub.3     "        "        "                                            4-OCF.sub.3    "        "        "                                            4-SCF.sub.3    "        "        "                                            4-SCH.sub.3    "        "        "                                            4-C(CH.sub.3).sub.3                                                                          "        "        "                                             ##STR422##    CH.sub.2CH.sub.2                                                                        ##STR423##                                                                            N(CH)                                         ##STR424##    "        "        "                                             ##STR425##    "        "        "                                             ##STR426##    "        "        "                                             ##STR427##    "        "        "                                             ##STR428##    "        "        "                                             ##STR429##    "        "        "                                             ##STR430##    "        "        "                                            3,4-Cl.sub.2   "        "        "                                            4-CF.sub.3     "        "        "                                            4-OCF.sub.3    "        "        "                                            4-SCF.sub.3    "        "        "                                            4-SCH.sub.3    "        "        "                                            4-C(CH.sub.3).sub.3                                                                          "        "        "                                             ##STR431##    CHCH                                                                                    ##STR432##                                                                            N(CH)                                         ##STR433##    "        ""                                                     ##STR434##    "        "        "                                             ##STR435##    "        "        "                                             ##STR436##    "        "        "                                             ##STR437##    "        "        "                                             ##STR438##    "        "        "                                             ##STR439##    "        "        "                                            3,4-Cl.sub.2   "        "        "                                            4-CF.sub.3     "        "        "                                            4-OCF.sub.3    "        "        "                                            4-SCF.sub.3    "        "        "                                            4-SCH.sub.3    "        "        "                                            4-C(CH.sub.3).sub.3                                                                          "        "        "                                             ##STR440##    CH.sub.2CH.sub.2                                                                        ##STR441##                                                                            N(CH)                                         ##STR442##    "        "        "                                             ##STR443##    "        "        "                                             ##STR444##    "        "        "                                             ##STR445##    "        "        "                                             ##STR446##    "        "        "                                             ##STR447##    "        "        "                                             ##STR448##    "        "        "                                            3,4-Cl.sub.2   "        "        "                                            4-CF.sub.3     "        "        "                                            4-OCF.sub.3    "        "        "                                            4-SCF.sub.3    "        "        "                                            4-SCH.sub.3    "        "        "                                            4-C(CH.sub.3).sub.3                                                                          "        "        "                                             ##STR449##    CHCH     C(CH.sub.3).sub.3                                                                      N(CH)                                         ##STR450##    "        "        "                                             ##STR451##    "        "        "                                             ##STR452##    "        "        "                                             ##STR453##    "        "        "                                             ##STR454##    "        "        "                                             ##STR455##    "        "        "                                             ##STR456##    "        "        "                                            3,4-Cl.sub.2   "        "        "                                            4-CF.sub.3     "        "        "                                            4-OCF.sub.3    "        "        "                                            4-SCF.sub.3    "        "        "                                            4-SCH.sub.3    "        "        "                                            4-C(CH.sub.3).sub.3                                                                          "        "        "                                             ##STR457##    CHCH     CH(CH.sub.3).sub.2                                                                     N(CH)                                         ##STR458##    "        "        "                                             ##STR459##    "        "        "                                             ##STR460##    "        "        "                                             ##STR461##    "        "        "                                             ##STR462##    "        "        "                                             ##STR463##    "        "        "                                             ##STR464##    "        "        "                                            3,4-Cl.sub.2   "        "        "                                            4-CF.sub.3     "        "        "                                            4-OCF.sub.3    "        "        "                                            4-SCF.sub.3    "        "        "                                            4-SCH.sub.3    "        "        "                                            4-C(CH.sub.3).sub.3                                                                          "        "        "                                             ##STR465##    CHCH                                                                                    ##STR466##                                                                            N(CH)                                         ##STR467##    "        "        "                                             ##STR468##    "        "        "                                             ##STR469##    "        "        "                                             ##STR470##    "        "        "                                             ##STR471##    "        "        "                                             ##STR472##    "        "        "                                             ##STR473##    "        "        "                                            3,4-Cl.sub.2   "        "        "                                            4-CF.sub.3     "        "        "                                            4-OCF.sub.3    "        "        "                                            4-SCF.sub.3    "        "        "                                            4-SCH.sub.3    "        "        "                                            4-C(CH.sub.3).sub.3                                                                          "        "        "                                             ##STR474##    CHCH                                                                                    ##STR475##                                                                            N(CH)                                         ##STR476##    "        "        "                                             ##STR477##    "        "        "                                             ##STR478##    "        "        "                                             ##STR479##    "        "        "                                             ##STR480##    "        "        "                                             ##STR481##    "        "        "                                             ##STR482##    "        "        "                                            3,4-Cl.sub.2   "        "        "                                            4-CF.sub.3     "        "        "                                            4-OCF.sub.3    "        "        "                                            4-SCF.sub.3    "        "        "                                            4-SCH.sub.3    "        "        "                                            4-C(CH.sub.3).sub.3                                                                          "        "        "                                            4-Cl           OCH.sub.2                                                                              CH(CH.sub.3).sub.2                                                                     N(CH)                                        4-F            "        "        "                                            4-CH.sub.3     "        "        "                                            4-Cl           OCH.sub.2                                                                               ##STR483##                                                                            "                                            4-F            "        "        "                                            4-CH.sub.3     "        "        "                                            4-Cl           OCH.sub.2                                                                               ##STR484##                                                                            "                                            4-F            "        "        "                                            4-CH.sub.3     "        "        "                                            4-Cl           CH.sub.2CH.sub.2                                                                       CH(CH.sub.3).sub.2                                                                     "                                            4-F            "        "        "                                            4-CH.sub.3     "        "        "                                            4-Cl           CH.sub.2CH.sub.2                                                                        ##STR485##                                                                            N(CH)                                        4-F            "        "        "                                            4-CH.sub.3     "        "        "                                            4-Cl           CH.sub.2CH.sub.2                                                                        ##STR486##                                                                            "                                            4-F            "        "        "                                            4-CH.sub.3     "        "        "                                            4-Cl           CHCH     CH(CH.sub.3).sub.2                                                                     "                                            4-F            "        "        "                                            4-CH.sub.3     "        "        "                                            4-Cl           CHCH                                                                                    ##STR487##                                                                            "                                            4-F            "        "        "                                            4-CH.sub.3     "        "        "                                            4-Cl           CHCH                                                                                    ##STR488##                                                                            N(CH)                                        4-F            "        "        "                                            4-CH.sub.3     "        "        "                                            2,4-Cl.sub.2   CH.sub.2CH.sub.2                                                                       C(CH.sub.3).sub.3                                                                      "                                            4-CH.sub.3     "        "        "                                            4-Cl, 2-CH.sub.3                                                                             "        "        "                                            2,4-Cl.sub.2   CHCH     C(CH.sub.3).sub.3                                                                      "                                            4-CH.sub.3     "        "        "                                            4-Cl, 2-CH.sub.3                                                                             "        "        "                                            4-F            OCH.sub.2                                                                              C(CH.sub.3).sub.3                                                                      "                                            2-CH.sub.3     CH.sub.2CH.sub.2                                                                       C(CH.sub.3).sub.3                                                                      N                                            4-F            CHCH     C(CH.sub.3).sub.3                                                                      N                                            __________________________________________________________________________

Further particularly preferred azoles of the formula (V) are mentionedin the preparative examples hereinbelow.

The azoles of the formula (V) are hitherto unknown. However, they can beprepared by reacting an oxirane of the general formula ##STR489## inwhich

R¹³, Y², Z and m have the meanings given above, with an azole of thegeneral formula ##STR490## in which

X² has the meaning given above, at a temperature between 60° C. and 150°C. in the presence of a diluent and, if appropriate, in the presence ofan acidbinding agent.

Preferred pyrimidine butanol derivatives of the formula (VI), are those,in which

R¹⁴ represents a hydrogen, fluorine, chlorine or bromine atom, an alkylradical having 1 to 4 carbon atoms or a benzyloxy radical which isoptionally substituted by chlorine, and

R¹⁵ represents a hydrogen, fluorine, chlorine or bromine atom.

Very particularly preferred compounds of the formula (VI) are those inwhich,

R¹⁴ represents a hydrogen, fluorine or chlorine atom or a methyl, ethyl,isopropyl, methoxy, ethoxy, isopropoxy, benzyloxy or chlorobenzyloxyradical and

R¹⁵ represents a hydrogen, chlorine or fluorine atom.

Further specific particularly preferred pyrimidine-butanol derivativesof the formula (VI) are given in the preparative examples hereinbelow.

The pyrimidine-butanol derivatives of the formula (VI) are already known(see DE-A (German Published Specification) 2,742,173).

The following preferred acids which are suitable for the preparation ofacid addition salts of azoles of the formulae (I), (II), (III), (IV) and(V): the hydrohalic acids (such as hydrochloric acid and hydrobromicacid), phosphoric acid, nitric acid, sulphuric acid, monofunctional andbifunctional carboxylic acids and hydroxycarboxylic acids (such asacetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid,citric acid, salicylic acid, sorbic acid and lactic acid) and sulphonicacids (such as p-toluenesulphonic acid and 1,5-naphthalenedisulphonicacid).

The acid addition salts of the compounds of the formulae (I) to (V) canbe obtained in a simple manner according to customary methods of saltformation, for example by dissolving a compound of the formulae (I) to(V) in a suitable inert solvent and adding the acid, for examplehydrochloric acid, and can be isolated in a known manner, for example byfiltering off, and, if appropriate, can be purified by washing with aninert organic solvent.

Salts of metals of the main groups II to IV and sub-groups I, II and IVto VIII of the periodic system of the elements are preferred salts forthe preparation of metal salt complexes of the compounds of the formulae(I) to (V), copper, zinc, manganese, magnesium, tin, iron and nickelbeing mentioned by way of example.

Anions which are preferably derived from the following acids aresuitable anions of the salts: hydrohalic acids (such as hydrochloricacid and hydrobromic acid), phosphoric acid, nitric acid and sulphuricacid.

The metal complexes of compounds of the formulae (I) to (V) can beobtained in a simple manner according to customary processes, forexample by dissolving the metal salt in alcohol, for example ethanol,and adding the solution to a compound of the formulae (I) to (V). Themetal salt complexes can be isolated in a known manner, for example byfiltering off, and, if appropriate, can be purified byrecrystallization.

Preferred phosphonic acid derivatives of the formula (VII) are those inwhich R¹⁶ and R¹⁷ represent a hydrogen atom or a sodium cation.

The phosphonic acid derivatives of the formula (VII) are already known(see DE-A (German Published Specification) 2,053,967).

Preferred 1-amino-cyclopropane-1-carboxylic acid derivatives of theformula (VIII) are those in which

R¹⁸ represents a hydroxyl radical, an alkoxy radical having 1 to 20carbon atoms, a benzyloxy or amino radical, an alkylamino radical having1 to 4 carbon atoms, a dialkylamino radical having 1 to 4 carbon atomsper alkyl radical, or a radical

    O.sup.⊖ M.sup.⊕

wherein

M.sup.⊕ represents a sodium ion or potassium ion, a magnesium ionequivalent or calcium ion equivalent, ammonium, alkylammonium having 1to 4 carbon atoms, or dialkylammonium, trialkylammonium ortetraalkylammonium having 1 to 4 carbon atoms per alkyl radical in eachcase, and

R¹⁹ represents an amino radical or a radical of the general formula--NH--CO--R,

wherein

R represents a hydrogen atom an alkyl radical having 1 to 4 carbon atomsor a phenyl radical, or a radical --N.sup.⊕ H₃ Cl.sup.⊖.

Very particularly preferred compounds of the formula (VIII) are those inwhich

R¹⁸ represents a hydroxyl radical, an alkoxy radical having 1 to 10carbon atoms, a benzyloxy or amino radical, an alkylamino radical having1 or 2 carbon atoms, a dialkylamino radical having 1 or 2 carbon atomsper alkyl radical, or a radical

    O.sup.⊖ M.sup.⊕

wherein

M.sup.⊕ represents a sodium ion or potassium ion, a magnesium ionequivalent or calcium ion equivalent, ammonium, alkylammonium having 1or 2 carbon atoms, or dialkylammonium, trialkylammonium ortetraalkylammonium having 1 or 2 carbon atoms per alkyl radical in eachcase, and

R¹⁹ represents amino, formylamino, acetylamino, propionylamino orN.sup.⊕ H₃ Cl.sup.⊖.

Further particularly preferred 1-amino-cyclopropane-1-carboxylic acidderivatives of the formula (VIII) are mentioned in the preparativeexamples hereinbelow.

The 1-amino-cyclopropane-1-carboxylic acid derivatives of the formula(VIII) are already known (see U.S. Pat. No. 4,236,983 issued Dec. 2,1980.

If the active compounds are present in the active compound combinationsaccording to the invention in certain proportions, the synergisticeffect is particularly clearly exhibited. However, the proportions byweight of the active compounds in the active compound combinations canvary within relatively wide ranges. In general, 0.05 to 5 parts byweight, preferably 0.1 to 4 parts by weight, of one of the activecompounds listed under (2) are present for 1 part by weight of an activecompound listed under (1).

The active compound combinations according to the invention exhibit apowerful plant-growth inhibiting activity, particularly in the case ofmonocotyledonous plants, such as, for example, cereals and grass.

Inhibiting the growth in length of cereals is important because lodgingof the stems of the cereal is thereby largely avoided, even underunfavorable weather conditions. By using the active compoundcombinations according to the invention, it is also possible to apply afertilizer containing greater quantities of nitrogenous fertilizers,without danger of the cereal lodging. Thus, by using the active compoundcombinations according to the invention in conjunction with theapplication of a larger quantity of fertilizer, greater yields can beachieved.

The synergistic effect of the active compound combinations according tothe invention, which effect has been described, can also beadvantageously utilized for inhibiting the growth of grass. It is thuspossible, for example, to reduce the frequency of cutting the grass inornamental gardens, parks and athletic fields or at borders.

Cereals are to be understood in the present case as meaning allcustomary cereal types. These preferably include oats, rye, barley,wheat and rice.

The active compound combinations can be converted to the customaryformulations, such as solutions, emulsions, suspensions, powders andgranules.

The preferred time of application of the growth regulators depends onthe climatic and vegetative circumstances.

The foregoing description should not be taken as implying that each ofthe compounds can exhibit all of the described effects on plants. Theeffect exhibited by a compound in any particular set of circumstancesmust be determined empirically.

These formulations may be produced in known manner, for example bymixing the active compounds with extenders, that is to say liquid orliquefied gaseous or solid diluents or carriers, optionally with the useof surface-active agents, that is to say emulsifying agents and/ordispersing agents and/or foam-forming agents. In the case of the use ofwater as an extender, organic solvents can, for example, also be used asauxiliary solvents.

As liquid diluents or carriers, especially solvents, there are suitablein the main, aromatic hydrocarbons, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane orparaffins, for example mineral oil fractions, alcohols, such as butanolor glycol as well as their ethers and esters, ketones, such as acetone,methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, orstrongly polar solvents, such as dimethylformamide anddimethylsulphoxide, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which wouldbe gaseous at normal temperature and under normal pressure, for exampleaerosol propellants, such as halogenated hydrocarbons as well as butane,propane, nitrogen and carbon dioxide.

As solid carriers there may be used ground natural minerals, such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals, such ashighly-dispersed silicic acid, alumina and silicates. As solid carriersfor granules there may be used crushed and fractionated natural rockssuch as calcite, marble, pumice, sepiolite and dolomite, as well assynthetic granules of inorganic and organic meals, and granules oforganic materials such as sawdust, coconut shells, corn cobs and tobaccostalks.

As emulsifying and/or foam-forming agents there may be used non-ionicand anionic emulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products. Dispersing agents include, for example,lignin sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, can be used in theformulations.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs or metal phthalocyaninedyestuffs, and trace nutrients, such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain from 0.1 to 95 percent by weight oftotal active ingredients, preferably from 0.5 to 90 percent by weight.

The active compound combinations according to the invention can bepresent in the formulations as a mixture with other known activecompounds, such as fungicides, insecticides, acaricides and herbicides,and also as mixtures with fertilizers.

The active compound combinations can be used as such, in the form oftheir formulations or as the use forms prepared therefrom, such asready-to-use solutions, emulsifiable concentrates, emulsions,suspensions, wettable powders, soluble powders and granules.

They are used in the customary manner, for example by watering,spraying, atomizing and scattering.

The active compound concentrations can be varied within a substantialrange. In general, 0.01 to 50 kg, preferably, 0.05 to 10 kg, of theactive compound are employed per hectare of soil surface.

The present invention also provides a method of regulating the growth ofplants which comprises applying to the plants, or to a habitat thereof,a composition of the present invention.

The present invention further provides plants, the growth of which hasbeen regulated by their being grown in areas in which immediately priorto and/or during the time of the growing a composition of the presentinvention was applied.

It will be seen that the usual methods of providing a harvested crop maybe improved by the present invention.

The good plant-inhibiting action of the active compound combinationsaccording to the invention can be seen from the examples which follow.While the individual active compounds have weaknesses ingrowth-inhibiting action, the combinations show an action which goesbeyond a simple additive action.

A synergistic effect exists with growth inhibitors whenever thegrowth-inhibiting action of the active compound combinations is greaterthan the sum of the actions of the individually applied activecompounds.

The action to be expected for a given combination of two growthinhibitors can (see Colby, S. R., "Calculating synergistic andantagonistic responses of herbicide combinations", Weeds 15, pages20-22, 1967) be calculated as follows:

if X=% growth inhibition by active compound A used in an amount of pkg/ha,

and Y=% growth inhibition by active compound B used in an amount of qkg/ha,

and E=the expected growth inhibition by the active compounds A and Bused in amounts of p and q kg/ha,

then ##EQU1##

If the actual growth inhibition is greater than calculated, the actionof the combination is superadditive, that is to say a synergistic effectexists.

The tables in Examples A and B show clearly that the foundgrowth-inhibiting action of the active compound combinations accordingto the invention is greater than the calculated action, that is to say asynergistic effect exists.

The active compounds indicated below are employed in the examples whichfollow: ##STR491##

EXAMPLE A

Inhibition of growth of barley

Solvent: 30 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate

To produce a suitable preparation of active compound, 1 part by weightof the active compounds was mixed with the stated amounts of solvent andemulsifier and the mixture was made up to the desired concentration withwater.

Barley plants were grown in a greenhouse to the 2-leaf stage. In thisstage, the plants were sprayed with the equivalent of 500 l/ha of thepreparations of active compound. After 11 days, the additional growthwas measured on all plants and the inhibition of growth in per cent ofthe additional growth of the control plants was calculated. 100%inhibition of growth meant that growth had stopped and 0% denoted agrowth corresponding to that of the control plants.

Active compounds, quantities used and test results are indicated in thetable which follows.

                  TABLE A                                                         ______________________________________                                        Inhibition of growth of barley                                                           Quantity of                                                        Active com-                                                                              active com-   Inhibition of                                        pounds or  pound used    growth in %                                          combinations                                                                             kg/ha         found*  calc.*                                       ______________________________________                                        (VIII-17)  1                   13    --                                       (VII-1)    1                   12    --                                       (I-1)      4                   13    --                                       (I-1)      4                                                                             +                   29    23.4                                     (VII-1)    1                                                                  (V-1)      2                   19    --                                       (V-1)      2                                                                             +                   50    28.7                                     (VII-1)    1                                                                  (I-2)      2                   17    --                                       (I-2)      2                                                                             +                   35    27.0                                     (VII-1)    1                                                                  (III-4)    2                   8     --                                       (IIII-4)   2                                                                             +                   31    20.0                                     (VIII-17)  1                                                                  (II-2)     2                   17    --                                       (II-2)     2                                                                             +                   35    27.8                                     (VIII-17)  1                                                                  (II-2)     2                                                                             +                   37    27.0                                     (VII-1)    1                                                                  ______________________________________                                         *found = inhibition of growth found                                           *calc. = inhibition of growth calculated using the formula given              hereinabove                                                              

EXAMPLE B

Inhibition of growth of barley

Solvent: 30 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate

To produce a suitable preparation of active compound, 1 part by weightof the active compounds was mixed with the stated amounts of solvent andemulsifier and the mixture was made up to the desired concentration withwater.

Barley plants were grown in a greenhouse to the 2-leaf stage. In thisstage, the plants were sprayed with the equivalent of 500 l/ha of thepreparations of active compound. After 24 days, the additional growthwas measured on all plants and the inhibition of growth in percent ofthe additional growth of the control plants was calculated. 100%inhibition of growth meant that growth had stopped and 0% denoted agrowth corresponding to that of the control plants.

Active compounds, quantities used and test results are indicated in thetable which follows.

                  TABLE B                                                         ______________________________________                                        Inhibition of growth of barley                                                           Quantity of                                                        Active com-                                                                              active com-   Inhibition of                                        pounds or  pound used    growth in %                                          combinations                                                                             kg/ha         found*  calc.*                                       ______________________________________                                        (VIII-17)  1                 3     --                                         (VII-1)    1                 2     --                                         (VI-4)     2                 25    --                                         (VI-4)     2                                                                             +                 31    27.3                                       (VIII-17)  1                                                                  (V-1)      2                 1     --                                         (V-1)      2                                                                             +                 22    10.8                                       (VII-1)    1                                                                  (I-2)      2                 5     --                                         (I-2)      2                                                                             +                 17    6.9                                        (VII-1)    1                                                                  (I-3)      2                 19    --                                         (I-3)      2                                                                             +                 25    20.6                                       (VII-1)    1                                                                  (III-1)    2                 22    --                                         (III-1)    2                                                                             +                 33    24.3                                       (VIII-17)  1                                                                  (II-2)     2                 5     --                                         (II-2)     2                                                                             +                 33    7.9                                        (VIII-17)  1                                                                  (II-2)     2                                                                             +                 26    6.9                                        (VII-1)    1                                                                  ______________________________________                                         *found = inhibition of growth found                                           *calc. = inhibition of growth calculated using the formula given              hereinabove                                                              

EXAMPLE C

Inhibition of growth of barley

Aqueous solutions containing 1% by weight of active compound wereprepared by mixing the required amount of the formulations, which aredescribed in the formulation examples I to III, with water. Said aqueoussolutions were mixed in the desired amounts and diluted with water untilthe desired concentration was reached.

Barley plants (variety "Gerda") were grown in Neubauer pots (8 plantsper pot) in the field. In the 2-node-stage, the plants were sprayed withthe equivalent of 500 l/ha of the preparations of the active compounds.After 2 months, the additional growth was measured on all plants and theinhibition of growth in percent of the additional growth of the controlplants was calculated. 100% inhibition of growth meant that growth hadstopped and 0% denoted a growth corresponding to that of the controlplants.

Active compounds, quantities used and test results are indicated in thetable which follows.

                  TABLE C                                                         ______________________________________                                        Inhibition of growth of barley                                                             quantity of active                                                                          Inhibition of growth                               Active compounds or                                                                        compounds used                                                                              in %                                               combinations kg/ha         found*   calc.*                                    ______________________________________                                        (II-2)       0.25          5        --                                                     0.5           9        --                                        (VIII-3)     0.5           8        --                                        (II-2)       0.25                                                             +            +             21       12.6                                      (VIII-3)     0.5                                                                           0.5                                                                           +             24       16.28                                                  0.5                                                              (II-2)       0.125         0        --                                        (VIII-22)    0.5           12       --                                        (II-2)       0.125                                                            +            +             19       12                                        (VIII-22)    0.5                                                              ______________________________________                                         *found = inhibition of growth found                                           *calc. = inhibition of growth calculated using the formula given              hereinabove                                                              

Formulation Examples EXAMPLE I

For the formulation of a wettable powder

70% by weight of the active compound according to Example (II-2),

2% by weight of a surface active agent,

3% by weight of a dispersing agent on basis of ligninsulphonate,

5% by weight of a product obtained by condensation of cyclohexanone,formaldehyde and sodiumbisulphite,

5% by weight of a highly dispersed silicic acid and

15% by weight of kaolin

were thoroughly mixed in a Lodige-mixer and then were finely ground in aMikronizer 8".

EXAMPLE II

For the preparation of an emulsifiable concentrate

19.6% by weight of the active compound according to Example (VIII-3),

5.0% by weight of alkylarylpolyglycolether and

75.4% by weight of dimethylformamide

were thoroughly mixed.

EXAMPLE III

For the preparation of an emulsifiable concentrate

30.6% by weight of the active compound according to Example (VIII-22),

10.0% by weight of a surface active agent,

5.0% by weight of alkylarylpolyglycolether and

54.4% by weight of cyclohexanone

were thoroughly mixed.

Preparative Examples EXAMPLE (I-1) ##STR492##

The compound was prepared according to the instructions given in DE-A(German Published Specification) 2,407,143.

EXAMPLE (I-2) ##STR493##

The compound was prepared according to the instructions given in DE-A(German Published Specification) 2,737,489.

EXAMPLE (I-3) ##STR494##

The compound was prepared according to the instructions given in U.S.application Ser. No. 213,705 filed Dec. 5, 1980, now pending.

The azoles listed in Table 1 which follows were prepared in acorresponding manner.

                  TABLE 1                                                         ______________________________________                                         ##STR495##                                                                                                     Melting                                     Example                           point                                       No.     R.sup.1        X.sup.3                                                                             Y.sup.3                                                                            (°C.)                                ______________________________________                                        I-4                                                                                    ##STR496##    H     F    116-121                                     I-5                                                                                    ##STR497##    H     F    158-174                                     I-6                                                                                    ##STR498##    H     F    108-112                                     I-7                                                                                    ##STR499##    H     F    116-122                                     I-8                                                                                    ##STR500##    H     F    78-88                                       I-9                                                                                    ##STR501##    H     F    76-84                                       I-10                                                                                   ##STR502##    H     F    143-154  (decomposition)                    I-11                                                                                   ##STR503##    H     F    62-72                                       I-12                                                                                   ##STR504##    H     F    108-128  (decomposition)                    I-13                                                                                   ##STR505##    F     F    92-111                                      I-14                                                                                   ##STR506##    H     Cl   82-88                                       I-15                                                                                   ##STR507##    F     F    156-168  (decomposition)                    I-16                                                                                   ##STR508##    H     Cl   98-104                                      I-17                                                                                   ##STR509##    F     F    108-126  (decomposition)                    I-18                                                                                   ##STR510##    H     Cl   108-112                                     I-19                                                                                   ##STR511##    H     F    141-144                                     I-20                                                                                   ##STR512##    H     F    73-76                                       I-21                                                                                   ##STR513##    H     F    86-92                                       I-22                                                                                   ##STR514##    H     F    63-68                                       I-23                                                                                   ##STR515##    H     Cl   108-121                                     I-24                                                                                   ##STR516##    H     F    72-112                                      I-25                                                                                   ##STR517##    H     F    88-98                                       I-26                                                                                   ##STR518##    H     F    112-123                                     I-27                                                                                   ##STR519##    H     Cl   semi-  crystalline                          I-28                                                                                   ##STR520##    Cl    Cl   semi-  crystalline                          I-29                                                                                   ##STR521##    Cl    Cl   136-137                                     I-30                                                                                   ##STR522##    H     F    90-108                                      I-31                                                                                   ##STR523##    H     H    143-146                                     ______________________________________                                    

The azoles listed in Table 2 which follows were also prepared accordingto the method described in Example (I-3).

                  TABLE 2                                                         ______________________________________                                         ##STR524##                   (Ia)                                                                              Melting                                     Example                           point                                       No.     R.sup.1        X.sup.3                                                                             Y.sup.3                                                                            (°C.)                                ______________________________________                                        I-32                                                                                   ##STR525##    H     F    78-79                                       I-33                                                                                   ##STR526##    H     F    112-120                                     I-34                                                                                   ##STR527##    H     F    62-72                                       I-35                                                                                   ##STR528##    H     F    58-70                                       I-36                                                                                   ##STR529##    H     F    150 (decom-  position)  (× HCl)       I-37                                                                                   ##STR530##    H     F    80-92                                       I-38                                                                                   ##STR531##    H     F    138-140                                     I-39                                                                                   ##STR532##    H     F    94                                          I-40                                                                                   ##STR533##    H     F    182  (decomposition)  (× HCl)         I-41                                                                                   ##STR534##    H     F    99                                          I-42                                                                                   ##STR535##    H     Cl   102                                         I-43                                                                                   ##STR536##    F     F    108                                         I-44                                                                                   ##STR537##    Cl    Cl   Oil                                         I-45                                                                                   ##STR538##    F     F    Oil                                         I-46                                                                                   ##STR539##    F     F    63-78                                       I-47                                                                                   ##STR540##    F     F    96-112  (decomposition)   (×                                            HCl)                                        I-48                                                                                   ##STR541##    H     Cl   116-127  (decomposition)  (×                                            HCl)                                        I-49                                                                                   ##STR542##    H     Cl   58-78                                       I-50                                                                                   ##STR543##    H     Cl   58-74                                       I-51                                                                                   ##STR544##    H     F    78                                          I-52                                                                                   ##STR545##    H     Cl   56                                          I-53                                                                                   ##STR546##    H     F    82                                          I-54                                                                                   ##STR547##    H     F    86                                          I-55                                                                                   ##STR548##    H     F    88                                          I-56                                                                                   ##STR549##    H     F    46-48                                       I-57                                                                                   ##STR550##    H     F    53-63                                       I-58                                                                                   ##STR551##    H     F    62-64                                       I-59                                                                                   ##STR552##    Cl    Cl   Cil                                         I-60                                                                                   ##STR553##    H     F    78-81                                       I-61                                                                                   ##STR554##    H     F    138-141                                     ______________________________________                                    

EXAMPLE (II-1) ##STR555##

83.5 g (0.5 mol) of pinacolyl-1,2,4-triazole, 60 g (0.54 mol) ofcyclohexanaldehyde, 4.2 g (0.05 mol) of piperidine and 6 g (0.1 mol) ofglacial acetic acid in 300 ml of toluene were heated under reflux in awater separator until water no longer passed over. After the reactionsolution had cooled, it was washed with saturated sodium chloridesolution, and the organic phase was dried over sodium sulphate, filteredand concentrated. The residue was taken up in 500 ml of acetone, and afiltered solution of 90 g (0.25 mol) of naphthalene-1,5-disulphonic acidin 500 ml of acetone was added, while stirring.

The precipitate which first separated out was filtered off undersuction, the filtrate was further concentrated and the colorlesscrystalline residue obtained was taken up in 500 ml of methylenechloride. Semiconcentrated sodium carbonate solution was thereafteradded to the mixture until an alkaline reaction was obtained. Theorganic phase was separated off, dried, filtered and concentrated. Theoleaginous residue was taken up in petroleum ether and was left tocrystallize. 64 g (49% of theory) of1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-en-3-one ofmelting point 98° C. were obtained.

EXAMPLE (II-2) ##STR556##

26 g (0.1 mol) of1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-en-3-one(preparedas described in Example II-1) were taken up in 200 methanol, and 4.5 gof sodium borohydride were added in portions to the solution, whilestirring and cooling. After the reaction had ended, the reaction mixturewas adjusted to pH 6 and was concentrated. The residue was taken up in200 ml of methylene chloride, and the solution was washed with saturatedsodium bicarbonate solution, dried over sodium sulphate, filtered andconcentrated. The residue was recrystallized from petroleum ether. 14.5g (55% of theory) of1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-en-3-ol ofmelting point 131° C. were obtained.

EXAMPLE (II-3) ##STR557##

A solution of 26.3 g (0.1 mol) of1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-en-3-ol(prepared as described in Example II-2) in 50 ml of dioxane was addeddropwise to a suspension of 3 g of 80% strength sodium hydride in 100 mlof dioxane. After the addition had ended, the mixture was warmed to 50°C. for 1 hour. After the mixture had cooled, 10.9 g (0.1 mol) of ethylbromide were added dropwise to it, and the reaction mixture was heatedunder reflux overnight. After the mixture had cooled, 10 ml of methanolwere added to it and it was concentrated in a rotary evaporator. Theresidue was taken up in methylene chloride and was washed with water.After the organic phase had been dried over sodium sulphate, it wasfiltered and the filtrate was concentrated. The residue was distilled.11.0 g (37.8% of theory) of1-cyclohexyl-3-ethoxy-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent- 1-ene ofboiling point 110° C./0.07 mm Hg were obtained.

EXAMPLE (II-4) ##STR558##

A solution of 13.15 g (0.05 mol) of1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-en-3-ol(prepared as described in Example II-2) in 50 ml of dioxane was addeddropwise to a suspension of 1.5 g of 80% strength sodium hydride in 50ml of dioxane. After the evolution of hydrogen had ceased, 3.9 g (0.05mol) of acetyl chloride were added dropwise to the mixture. The mixturewas heated under reflux for 4 hours. After the mixture had cooled, thesolvent was distilled off in vacuo, and the residue was taken up inmethylene chloride and the solution was extracted with water. Theorganic phase was dried over sodium sulphate and filtered, and thesolution was concentrated. The residue was purified over a column(silica gel; methanol: chloroform=1:3). 5.6 g (35.4% of theory) of3-acetoxy-1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-enewere obtained as a slightly yellow oil.

2 ml of pyridine were added to a solution of 13.15 g (0.05 mol) of1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-en-3-ol(prepared as described in Example II-2) in 100 ml of acetic anhydride.The mixture was stirred for four hours at 70° C. The reaction mixturewas thereafter poured onto water and was neutralized with sodiumbicarbonate. The aqueous phase was extracted several times with ether.The combined ether phases were dried over sodium sulphate andconcentrated. 11.2 g (70.8% of theory) of3-acetoxy-1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-enewere obtained as a slightly yellow oil.

EXAMPLE (II-5) ##STR559##

6.5 g (0.055 mol) of phenyl isocyanate and three drops of tributyltinlaurate as a catalyst were added to a solution of 13.15 g (0.05 mol) of1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-en-3-ol(prepared as described in Example II-2) in 100 ml of ether. The mixturewas stirred for 5 days at room temperature. After the solvent had beendistilled off in vacuo, the residue was recrystallized from ethylacetate/ligroin. 4.8 g (25.1% of theory) of1-cyclohexyl-4,4-dimethyl-3-phenylcarbamoyloxy-2-(1,2,4-triazol-1-yl)-pent-1-eneof melting point 156° C. were obtained.

The compounds below were obtained in an analogous manner:

                                      TABLE 3                                     __________________________________________________________________________     ##STR560##                                                 (IId)             Example                                           Melting                     No.  R.sup.3          X.sup.1           R.sup.4                                                                            R.sup.5                                                                            point                       __________________________________________________________________________                                                      (°C.)                II-6 (CH.sub.3).sub.3 C                                                                             CO                                                                                               ##STR561##                                                                             193 (× 1/2 NDA)       II-7 (CH.sub.3).sub.3 C                                                                             CO                                                                                               ##STR562##                                                                             40-48                       II-8 (CH.sub.3).sub.3 C                                                                             CO                                                                                               ##STR563##                                                                             49                          II-9 (CH.sub.3).sub.3 C                                                                             CO                                                                                               ##STR564##                                                                             201 (× 1/2 NDA)       II-10                                                                              (CH.sub.3).sub.3 CO                n-C.sub.4 H.sub.9                                                                  C.sub.2 H.sub.5                                                                    Oil                         II-11                                                                              (CH.sub.3).sub. 3 C                                                                            CH(OH)                                                                                           ##STR565##                                                                             151 (Z Form)                II-12                                                                              (CH.sub.3).sub.3 C                                                                             CH(OH)                                                                                           ##STR566##                                                                             Oil                         II-13                                                                              (CH.sub.3).sub.3 C                                                                             CH(OC.sub.3 H.sub.7 -n)                                                                          ##STR567##                                                                             Oil                         II-14                                                                              (CH.sub.3).sub.3 C                                                                              ##STR568##                                                                                      ##STR569##                                                                             Oil                         II-15                                                                              (CH.sub.3).sub.3 C                                                                             CH(OCOCHCl.sub.2)                                                                                ##STR570##                                                                             Oil                         II-16                                                                              (CH.sub.3).sub.3 C                                                                              ##STR571##                                                                                      ##STR572##                                                                             Oil                         II-17                                                                               ##STR573##      CH(OH)                                                                                           ##STR574##                                                                             Oil                         II-18                                                                               ##STR575##      CH(OH)            C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                    Oil                         II-19                                                                               ##STR576##      CH(OH)                                                                                           ##STR577##                                                                             Oil                         II-20                                                                               ##STR578##      CH(OCOCH.sub.3)                                                                                  ##STR579##                                                                             Oil                         II-21                                                                              (CH.sub.3).sub.3 C                                                                             CCH.sub.3 (OH)                                                                                   ##STR580##                                                                             101                         II-22                                                                              (CH.sub.3).sub.3 C                                                                             CH(OH)                                                                                           ##STR581##                                                                             154 (.HCl) (Z Form)         II-23                                                                               ##STR582##      CH(OH)            C.sub.3 H.sub.7                                                                    CH.sub.3                                                                           Oil                         II-24                                                                              (CH.sub.3).sub.3 C                                                                             CH(OH)                                                                                           ##STR583##                                                                             110 (.CuCl.sub.2) (Z                                                          Form)                       II-25                                                                               ##STR584##      CH(OCONHCH.sub.3)                                                                                ##STR585##                                                                             62                          II-26                                                                               ##STR586##      CH(OH)            C.sub.2 H.sub.5                                                                    CH.sub.3                                                                           Oil                         II-27                                                                               ##STR587##                                                                                     ##STR588##       C.sub.3 H.sub.7                                                                    CH.sub.3                                                                           Oil                         II-28                                                                               ##STR589##      CH(OCOCH.sub.3)   C.sub.3 H.sub.7                                                                    CH.sub.3                                                                           Oil                         II-29                                                                              (CH.sub.3).sub.3 C                                                                              ##STR590##                                                                                      ##STR591##                                                                             Oil (Z Form)                II-30                                                                              ClCH.sub.2C(CH.sub.3).sub.2                                                                    CO                                                                                               ##STR592##                                                                             51                          II-31                                                                              ClCH.sub.2C(CH.sub.3).sub.2                                                                    CO                                                                                               ##STR593##                                                                             Oil                         II-32                                                                              ClCH.sub.2C(CH.sub.3).sub.2                                                                    CH(OH)                                                                                           ##STR594##                                                                             Oil                         II-33                                                                               ##STR595##      CH(OH)                                                                                           ##STR596##                                                                             156                         II-34                                                                              (CH.sub.3).sub.3 C                                                                             CH(OH)                                                                                           ##STR597##                                                                             153 (.HNO.sub.3) (Z                                                           Form)                       II-35                                                                               ##STR598##      CH(OH)                                                                                           ##STR599##                                                                             Oil                         II-36                                                                               ##STR600##      CH(OH)                                                                                           ##STR601##                                                                             Oil                         II-37                                                                               ##STR602##      CH(OH)                                                                                           ##STR603##                                                                             Oil                         II-38                                                                               ##STR604##      CH(OH)            C.sub.2 H.sub.5                                                                    CH.sub.3                                                                           Oil                         II-39                                                                               ##STR605##      CH(OH)            C.sub.2 H.sub.5                                                                    CH.sub.3                                                                           Oil                         II-40                                                                               ##STR606##      CH(OH)            C.sub.4 H.sub.9                                                                    C.sub.2 H.sub.5                                                                    Oil                         II-41                                                                              ClCH.sub.2C(CH.sub.3).sub.2                                                                    CH(OH)                                                                                           ##STR607##                                                                             Oil                         II-42                                                                              (CH.sub.3).sub.3 C                                                                             CH(OCH.sub.3)                                                                                    ##STR608##                                                                             63 (Z Form)                 II-43                                                                               ##STR609##      CH(OH)            C.sub.4 H.sub.9                                                                    C.sub.2 H.sub.5                                                                    Oil                         II-44                                                                              FCH.sub.2C(CH.sub.3).sub.2                                                                     CO                C.sub.4 H.sub.9                                                                    C.sub.2 H.sub.5                                                                    Oil                         II-45                                                                              (CH.sub.3).sub.3 C                                                                             CH(OCH.sub.3)                                                                                    ##STR610##                                                                             104 (E Form)                II-46                                                                              (CH.sub.3).sub.3 C                                                                             CH(OH)                                                                                           ##STR611##                                                                             137 (.HNO.sub.3) (E                                                           Form)                       II-47                                                                               ##STR612##      CH(OH)            CH.sub.3                                                                           CH.sub.3                                                                           187                         II-48                                                                              ClCH.sub.2C(CH.sub.3).sub.2                                                                    CH(OH)            CH.sub.3                                                                           CH.sub.3                                                                           Oil                         II-49                                                                              (CH.sub.3).sub.3 C                                                                             CH(OH)                                                                                           ##STR613##                                                                             242 (.1/2 NDA) (E                                                             Form)                       II-50                                                                              (CH.sub.3).sub.3 C                                                                             CH(OH)                                                                                           ##STR614##                                                                             168 (.CuCl.sub.2) (E                                                          Form)                       II-51                                                                              (CH.sub.3).sub.3 C                                                                             CO                                                                                               ##STR615##                                                                             137-140 (.CuCl.sub.2)                                                         (E Form)                    II-52                                                                               ##STR616##      CH(OH)                                                                                           ##STR617##                                                                             157                         II-53                                                                               ##STR618##      CH(OH)            C.sub.4 H.sub.9                                                                    C.sub.2 H.sub.5                                                                    118                         II-54                                                                              FCH.sub.2C(CH.sub.3).sub.2                                                                     CO                                                                                               ##STR619##                                                                             Oil                         II-55                                                                              FCH.sub.2C(CH.sub.3).sub.2                                                                     CO                                                                                               ##STR620##                                                                             Oil                         II-56                                                                              FCH.sub.2C(CH.sub.3).sub.2                                                                     CH(OH)                                                                                           ##STR621##                                                                             Oil                         II-57                                                                              FCH.sub.2C(CH.sub.3).sub.2                                                                     CH(OH)                                                                                           ##STR622##                                                                             Oil                         II-58                                                                              FCH.sub.2C(CH.sub.3).sub.2                                                                     CO                                                                                               ##STR623##                                                                             Oil (Z Form)                II-59                                                                              FCH.sub.2C(CH.sub.3).sub.2                                                                     CO                                                                                               ##STR624##                                                                             Oil (Z Form)                II-60                                                                              ClCH.sub.2C(CH.sub.3).sub.2                                                                    CO                                                                                               ##STR625##                                                                             103 (E Form)                II-61                                                                               ##STR626##      CH(OH)                      144                         II-62                                                                               ##STR627##      CH(OH)            C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                    148                         II-63                                                                              FCH.sub.2C(CH.sub.3).sub.2                                                                     CH(OH)                                                                                           ##STR628##                                                                             n.sub.D.sup.20 : 1.5049                                                       (Z Form)                    II-64                                                                              FCH.sub.2C(CH.sub.3).sub.2                                                                     CH(OH)                                                                                           ##STR629##                                                                             n.sub.D.sup.20 : 1.4910                                                       (Z Form)                    II-65                                                                              ClCH.sub.2C(CH.sub.3).sub.2                                                                    CH(OH)                                                                                           ##STR630##                                                                             n.sub.D.sup.20 : 1.5050                                                       (E Form)                    __________________________________________________________________________     E form and Z form = the two possible geometric isomeric forms                 NDA = 1,5Naphthalenedisulphonic acid                                     

EXAMPLE III-1 ##STR631##

The compound was prepared according to the method given in U.S.application Ser. No. 144,110 filed April 28, 1980, now pending.

EXAMPLE III-2 ##STR632## EXAMPLE III-3 ##STR633##

210.5 g (1 mol) of1-chloro-2,2-dimethyl-4-(1,2,4-triazol-1-yl)-butan-3-one, 140.5 g (1mol) of 4-chlorobenzaldehyde and 9.9 ml of piperidine and 30 g ofglacial acetic acid were heated under reflux in 300 ml of toluene for 8hours, the resulting water of reaction being removed azeotropically. Thereaction mixture was thereafter washed with water and with dilute sodiumbicarbonate solution, dried over sodium sulphate and concentrated invacuo. 305.9 g (94.4% of theory) of crude1-chloro-5-(4-chlorophenyl)-2,2-dimethyl-4-(1,2,4-triazol-1-yl)-4-penten-3-oneof boiling point 155° C./0.1 mm Hg were obtained as an E,Z isomermixture. The E isomer could be isolated in crystalline form by stirringthe isomer mixture with isopropanol or ethanol. It had a melting pointof 112° C.

EXAMPLE (III-4) ##STR634##

162 g (0.5 mol) of1-chloro-5-(4-chlorophenyl)-2,2-dimethyl-4-(1,2,4-triazol-1-yl)-4-penten-3-one(prepared as described in Example III-2) were dissolved in 500 ml ofisopropanol, and 9.5 g (0.25 mol) of sodium borohydride were added inportions to the solution, while stirring. The reaction mixture wasstirred for 10 hours at room temperature, and was then concentrated invacuo. The residue was taken up in toluene, and the solution was washedwith dilute acetic acid and then with water, and was dried over sodiumsulphate and concentrated in vacuo. 156.6 g (96% of theory) of1-chloro-5-(4-chlorophenyl)-2,2-dimethyl-4-(1,2,4-triazol-1-yl)-4-penten-3-olof refractive index n_(D) ²⁰ =1.5579 were obtained as an E/Z isomermixture.

EXAMPLE III-5 ##STR635##

48.6 g (0.15 mol) of1-chloro-5-(4-chlorophenyl)-2,2-dimethyl-4-(1,2,4-triazol-1-yl)-4-penten-3-one(prepared as described in Example III-2) and 30.6 g (0.15 mol) ofaluminum isopropylate were heated under reflux in 200 ml of isopropanolfor 7 hours, isopropanol and acetone being continuously distilled offover a 30 cm Vigreux column until acetone could no longer be detected inthe distillate. The reaction mixture was thereafter concentrated, andice/hydrochloric acid was added to the residue. The mixture wasextracted with methylene chloride. The combined methylene chlorideextracts were dried over sodium sulphate and concentrated in vacuo. Theoleaginous residue was separated by column chromatography (silicagel/chloroform). The unreduced E isomer of1-chloro-5-(4-chlorophenyl)-2,2-dimethyl-4-(1,2,4-triazol-1-yl)-penten-3-one(the compound given in Example III-2) and the Z isomer of pure1-chloro-5-(4-chlorophenyl)-2,2-dimethyl-4-(1,2,4-triazol-1-yl)-penten-3-olwith a melting point of 120° C. were obtained.

EXAMPLE (III-6) ##STR636##

2.0 g (6.13 mol) of the E isomer of1-chloro-5-(4-chlorophenyl)-2,2-dimethyl-4-(1,2,4-triazol-1-yl)-4-penten-3-one(prepared as described in Example III-3) and 0.467 g (4.11 mmol) ofcalcium chloride were dissolved in 30 ml of isopropanol, and a solutionof 0.167 g (4.3 mmol) of sodium borohydride was added dropwise to theabove solution at -5° C. After 6 hours, the reaction mixture was warmedto 25° C. and was concentrated in vacuo. The residue was poured ontowater, and the mixture was extracted with ethyl acetate. The combinedethyl acetate extracts were dried over sodium sulphate and concentratedin vacuo. The oleaginous residue crystallized on stirring it withdiisopropyl ether. 1.1 g (55% of theory) of1-chloro-5-(4-chlorophenyl)-2,2-dimethyl-4-(1,2,4-triazol-1-yl)-4-penten-3-olof melting point 170° C. were obtained as the E isomer.

The following compounds of the general formula (III) were obtained in acorresponding manner

                                      TABLE 3                                     __________________________________________________________________________     ##STR637##                        (IIIb)                                                                  Melting point (°C.)                       Example                      or refractive index                              No.   R.sup.9     Y.sup.1                                                                            X.sup.3                                                                          Y.sup.3                                                                          (n.sub.D.sup.20)                                 __________________________________________________________________________    III-7                                                                                ##STR638## CO   H  F  1.5672                                           III-8                                                                                ##STR639## CO   H  F  1.5565                                           III-9                                                                                ##STR640## CO   H  Cl 1.5655 (Z Isomer)                                III-10                                                                               ##STR641## CO   H  F  1.5632 (E Isomer)                                III-11                                                                               ##STR642## CH(OH)                                                                             H  F  230 (× NDA)                                III-12                                                                               ##STR643## CH(OH)                                                                             H  F  110 (Z Isomer)                                   III-13                                                                               ##STR644## CH(OH)                                                                             H  F  1.5250                                           III-14                                                                               ##STR645## CH(OH)                                                                             H  Cl 1.5820 (Z Isomer)                                III-15                                                                               ##STR646## CH(OH)                                                                             H  F  116 (Z Isomer)                                   III-16                                                                               ##STR647## CH(OH)                                                                             H  F  140 (E Isomer)                                   III-17                                                                               ##STR648## CH(OH)                                                                             H  F  150 (A Isomer)                                   III-18                                                                               ##STR649## CH(OH)                                                                             H  F  158 (E Isomer)                                   III-19                                                                               ##STR650## CO   F  F  1.5728                                           III-20                                                                               ##STR651## CO   F  F  1.5778                                           III-21                                                                               ##STR652## CO   Cl Cl 1.5942                                           III-22                                                                               ##STR653## CO   Cl Cl 1.5868                                           III-23                                                                               ##STR654## CH(OH)                                                                             F  F  74 (E Isomer)                                    III-24                                                                               ##STR655## CH(OH)                                                                             F  F  110 (Z Isomer)                                   III-25                                                                               ##STR656## CH(OH)                                                                             F  F  157 (E Isomer)                                   III-26                                                                               ##STR657## CH(OH)                                                                             F  F  154 (Z Isomer)                                   III-27                                                                               ##STR658## CH(OH)                                                                             Cl Cl 150 (Z Isomer)                                   III-28                                                                               ##STR659## CH(OH)                                                                             Cl Cl 148 (Z Isomer)                                   __________________________________________________________________________     NDA = 1,5Naphthalenedisulphonic acid                                     

EXAMPLE (V-1) ##STR660##

72.15 g (0.3 mol) of 2-(4-chlorophenoxy-methyl)-2-tert.-butyl-oxiraneand 24.15 g (0.35 mol) of 1,2,4-triazole were heated under reflux in 120ml of ethanol for 48 hours. The mixture was then concentrated, and theresidue was taken up in 200 ml of ethyl acetate and the solution heated.The solution was thereafter cooled in an ice bath, and the solidmaterial was filtered off under suction and was washed with ethylacetate. The filtrate was concentrated and the residue was dissolved inether/hexane, and the solution was treated with gaseous hydrogenchloride. The precipitate was filtered off under suction and washed withether, and the free base was obtained by the addition of ethylacetate/1N sodium hydroxide solution. 60.2 g (65% of theory) of2-(4-chlorophenoxy-methyl)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-olof melting point 84°-87° C. were obtained.

Preparation of the starting material ##STR661##

A solution of 162 ml (2.2 mols) of dimethyl sulphide in 400 ml ofabsolute acetonitrile was added to a solution of 189 ml (2.0 mols) ofdimethyl sulphate in 1,200 ml of absolute acetonitrile at roomtemperature. The reaction mixture was stirred overnight at roomtemperature. 118.8 g (2.2 mols) of sodium methylate were thereafteradded to the mixture. The mixture was stirred for 30 minutes, and asolution of 272 g (1.2 mols) of1-(4-chlorophenoxy)-3,3-dimethyl-butan-2-one in 600 ml of absoluteacetonitrile was added dropwise to it during the course of 30 minutes.The reaction mixture was further stirred overnight and was thenconcentrated, and the residue was partitioned between water and ethylacetate. The organic phase was separated off, washed twice with waterand once with saturated sodium chloride solution, dried over sodiumsulphate and concentrated, and the residue was distilled in vacuo. 242.4g (84% of theory) of 2-(4-chlorophenoxy-methyl)-2tert.-butyl-oxirane ofboiling point 115°-122° C./0.003 mm Hg and melting point 50°-52° C. wereobtained.

EXAMPLE (V-2) ##STR662##

8.02 g (0.1178 mol) of imidazole were added to 2.71 g (0.1178 mol) ofsodium in 250 ml of absolute ethanol. A solution of 14.17 g (0.0589 mol)of 2-(4-chlorophenoxy-methyl)-2-tert.-butyl-oxirane in 100 ml of ethanolwas added dropwise to the mixture at room temperature during the courseof 30 minutes. The reaction mixture was thereafter heated under refluxfor 8 hours and was concentrated, and the residue was taken up in ether.The ether solution was extracted three times with 1N hydrochloric acid,and the combined hydrochloric acid phases were neutralized with sodiumbicarbonate and then extracted with ethyl acetate. After the solutionhad been concentrated and the residue recrystallized from cyclohexane,11.6 g (64% of theory) of2-(4-chlorophenoxy-methyl)-3,3-dimethyl-1-(imidazol-1-yl)-butan-2-ol ofmelting point 154°-155° C. were obtained.

EXAMPLE (V-3) ##STR663##

A solution of 17.75 g (0.075 mol) of2-(4-chlorophenyl-ethenyl)-2-tert.-butyl-oxirane and 6.9 g (0.1 mol) of1,2,4-triazole in 30 ml of ethanol was heated in a bomb tube at 150° C.for 20 hours. The reaction mixture was thereafter concentrated, and thecrystalline residue was stirred with ether. The solid material was thenfiltered off under suction and was recrystallized from acetonitrile.17.7 g (77% of theory) of1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl)-1-penten-3-ol ofmelting point 139°-141° C. were obtained.

EXAMPLE (V-4) ##STR664##

A solution of 17.9 g (0.075 mol) of2-(4-chlorophenyl-ethyl)-2-tert.-butyl-oxirane and 6.9 g (0.1 mol) of1,2,4-triazole in 30 ml of ethanol was heated in a bomb tube at 150° C.for 20 hours. The reaction solution was allowed to cool and wasconcentrated. The residue was dissolved in ether, and the solution waswashed three times with water and once with sodium chloride solution,and was dried over sodium sulphate and concentrated. The residue wassubjected to chromatography over a silica gel column (eluent:dichloromethane/ethyl acetate 1:1). 12.3 g (53.2% of theory) of1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)-pentan-3-olwere obtained as a viscous oil.

The following compounds of the general formula (V) were obtained in ananalogous manner:

                                      TABLE 4                                     __________________________________________________________________________     ##STR665##                             (V)                                   Example                         Melting point                                 No.  Z.sub.m                                                                             Y.sup.2  R.sup.13 X.sup.2                                                                          (° C.)                                 __________________________________________________________________________    V-5  4-Cl, 2-CH.sub.3                                                                    OCH.sub.2                                                                              C(CH.sub.3).sub.3                                                                      N  125.5-29                                      V-6  2,4-Cl.sub.2                                                                        OCH.sub.2                                                                              C(CH.sub.3).sub.3                                                                      N  120.5-23.5                                    V-7  4-CH.sub.3                                                                          OCH.sub.2                                                                              C(CH.sub.3).sub.3                                                                      N  98-101.5                                      V-8  2-CH.sub.3                                                                          OCH.sub.2                                                                              C(CH.sub.3).sub.3                                                                      N  89 -101                                       V-9  4-F   CH.sub.2CH.sub.2                                                                       C(CH.sub.3).sub.3                                                                      N  91-95.5                                       V-10 2-CH.sub.3                                                                          CHCH     C(CH.sub.3).sub.3                                                                      N  Oil                                           V-11 4-Cl  CH.sub.2CH.sub.2                                                                       C(CH.sub.3).sub.3                                                                      N  212(decomposition)                                                            (× HCl)                                 V-12 2,4-Cl                                                                              OCH.sub.2                                                                              C(CH.sub.3).sub.3                                                                      CH 152-54                                        V-13 4-CH.sub.3                                                                          OCH.sub.2                                                                              C(CH.sub.3).sub.3                                                                      CH 129-31                                        V-14 2-CH.sub.3                                                                          OCH.sub.2                                                                              C(CH.sub.3).sub.3                                                                      CH 123-24                                        V-15 4-Cl, 2-CH.sub.3                                                                    OCH.sub.2                                                                              C(CH.sub.3).sub.3                                                                      CH 157-59                                        V-16 4-Cl  CH.sub.2CH.sub.2                                                                       C(CH.sub.3).sub.3                                                                      CH 157.5-59.5                                    V-17 4-F   CH.sub.2CH.sub.2                                                                       C(CH.sub.3).sub.3                                                                      CH 124-25                                        V-18 2-CH.sub.3                                                                          CH.sub.2CH.sub.2                                                                       C(CH.sub.3).sub.3                                                                      CH 94-99                                         V-19 4-Cl  CHCH     C(CH.sub.3).sub.3                                                                      CH 158-62                                        V-20 4-F   CHCH     C(CH.sub.3).sub.3                                                                      CH 144-46                                        V-21 2-CH.sub.3                                                                          CHCH     C(CH.sub.3).sub.3                                                                      CH 127-32                                        V-22 4-Cl  OCH.sub.2                                                                               ##STR666##                                                                            CH 216-17 (× 1/2 NDA)*                     V-23 4-CH.sub.3                                                                          CHCH     C(CH.sub.3).sub. 3                                                                     N  117-19                                        V-24 4-CH.sub.3                                                                          CHCH     C(CH.sub.3).sub.3                                                                      CH 144-46                                        V-25 2,6-Cl.sub.2                                                                        CHCH     C(CH.sub.3).sub.3                                                                      CH 110-16                                        V-26 4-CH.sub.3                                                                          CH.sub.2CH.sub.2                                                                       C(CH.sub.3).sub.3                                                                      N  Oil                                           __________________________________________________________________________     *NDA = 1,5Naphthalenedisulphonic acid                                    

EXAMPLE (VI-1) ##STR667##

A solution of 22.65 g (0.1 mol) of1-(4-chlorophenoxy)-3,3-dimethyl-butan-2-one in 110 ml of absolutetetrahydrofuran and 70 ml of absolute ether was cooled to -120° C. undera dry nitrogen atmosphere. A solution of 15.9 g (0.1 mol) of5-bromopyrimidine in 50 ml of absolute tetrahydrofuran was addeddropwise to the above solution. 50 ml of a 15% strength solution ofn-butyllithium in n-hexane was then slowly added dropwise to the mixtureat -120° C. The mixture was first stirred for 2 hours at a temperatureof approximately -110° C., and was thereafter stirred overnight at -78°C. The reaction mixture was warmed to room temperature and 100 ml of 10%strength ammonium chloride solution and 200 ml of ethyl acetate wereadded to it, and the aqueous phase was separated off. The organic phasewas washed successively once with 1N hydrochloric acid and twice withsaturated sodium chloride solution, and was dried over sodium sulphateand concentrated. The residue was suspended in ether, and the solidmaterial was filtered off under suction and recrystallized fromacetonitrile. 12.3 g (50% of theory relative to n-butyllithium) of1-(4-chlorophenoxy)-3,3-dimethyl-2-(pyrimidin-5-yl)-butan-2-ol ofmelting point 172°-174° C. were obtained.

The compounds of the formula ##STR668## which are listed in Table 5which follows, were obtained analogously:

                  TABLE 5                                                         ______________________________________                                        Example                           Melting                                     No.      R.sup.14        R.sup.15 point (° C.)                         ______________________________________                                        VI-2     H               H        127-129                                     VI-3     CH.sub.3 O      H        136-137                                     VI-4     F               H        163.5-164.5                                 VI-5     Cl              2-Cl     96-99                                       VI-6     Cl              3-Cl     155-157                                     VI-7     CH.sub.3        H        152-153.5                                   VI-8                                                                                    ##STR669##     H        122-124                                     ______________________________________                                    

EXAMPLE (VIII-1) ##STR670##

0.3 ml of concentrated hydrochloric acid and a solution of 5 g (0.04mol) of α-isocyanocyclopropanecarboxylic acid methyl ester in 10 ml ofmethanol were added successively to 40 ml of water at 20° C. Thereaction mixture was stirred for 6 hours and was then extracted withtwice 50 ml of methylene chloride. The organic phase was dried overmagnesium sulphate and filtered, and the solvent was distilled off invacuo. 4 g (70% of theory) of α-formylamino-cyclopropane-carboxylic acidmethyl ester remained as the residue in the form of a colorless liquid.Refractive index: n_(D) ²⁰ =1.4730.

EXAMPLE (VIII-2) ##STR671##

A solution of 3.1 g (0.55 mol) of potassium hydroxide in 50 ml ofethanol was added dropwise to a solution of 7 g (0.05 mol) ofα-isocyano-cyclopropanecarboxylic acid ethyl ester in 100 ml of ether at5° C. The mixture was stirred for 12 hours at 20° C. After the mixturehad been filtered under suction and the residue washed with ether, 6.4 g(86% of theory) of the potassium salt ofα-isocyano-cyclopropanecarboxylic acid were obtained as a white powder.

Melting point: 225° C.

1.18 g (0.066 mol) of water were added to a suspension of 9 g (0.06 mol)of the potassium salt of α-isocyano-cyclopropanecarboxylic acid in 50 mlof ethanol. The mixture was heated to the boil under reflux for 12hours, and after it had been cooled, 50 ml of ether were added to it at20° C. After the mixture had been filtered under suction, 7 g (70% oftheory) of the potassium salt of α-formylaminocyclopropanecarboxylicacid were obtained in the form of white crystals.

Melting point: 186° C.

EXAMPLE (VIII-3) ##STR672##

8.36 g (0.05 mol) of the potassium salt ofα-formylaminocyclopropanecarboxylic acid were dissolved in 20 ml ofwater, and 5 g (0.05 mol) of concentrated hydrochloric acid were addedto the solution at 0° C. The mixture was left to stand overnight at 5°C. After the mixture had been filtered under suction and the residuedried, 5.2 g (80% of theory) of α-formylaminocyclopropanecarboxylic acidwere obtained in the form of colorless crystals.

Melting point: 189° C.

EXAMPLE (VIII-4) ##STR673##

7.46 g (0.05 mol) of the potassium salt ofα-isocyanocyclopropanecarboxylic acid were added to a solution of 6.7 g(0.15 mol) of dimethylamine in 50 ml of water at 20° C., while stirring.After the reaction mixture had cooled to 5° C., 5 g (0.05 mol) ofconcentrated hydrochloric acid were added to it, and it was left tostand for 12 hours at 20° C. in a closed reaction vessel. The volatilecomponents were stripped off in the vacuum from a water jet, at a bathtemperature of 60° C. The product was extracted from the residue withmethylene chloride; the solution was dried with magnesium sulphate, and,after filtration, the solvent was distilled off in vacuo. 5.5 g (70% oftheory) of α-formylamino-cyclopropanecarboxylic acid N,N-dimethylamideremained, in the form of a pale yellow liquid.

Refractive index: n_(D) ²⁰ =1.4350.

EXAMPLE (VIII-5) ##STR674##

0.74 g (0.01 mol) of calcium hydroxide was added to a mixture of 2.5 g(0.02 mol) of α-formylaminocyclopropanecarboxylic acid and 40 ml ofethanol at 25° C., while stirring, and the mixture was then furtherstirred for 12 hours at room temperature. The solution was thenevaporated in vacuo, and the residue was triturated with ether. Afterthe mixture had been filtered under suction and the residue dried, 2.6 g(97% of theory) of the calcium salt ofα-formylamino-cyclopropanecarboxylic acid were obtained in the form of awhite powder.

Melting point: 290° C.

EXAMPLE (VIII-6) ##STR675##

A mixture of 19.4 g (0.15 mol) of α-formylaminocyclopropanecarboxylicacid and 200 ml of 18% strength hydrochloric acid was heated to the boilunder reflux for 3 hours. The mixture was then evaporated to dryness invacuo, and the residual solid was dried over phosphorus pentoxide in avacuum desiccator.

Yield: 18 g (92% of theory) of α-amino-cyclopropanecarboxylic acidhydrochloride.

Melting point: 232° C.

EXAMPLE (VIII-7) ##STR676##

3.1 g (0.022 mol) of benzoyl chloride were added to a mixture of 2 g(0.02 mol) of α-aminocyclopropanecarboxylic acid, 25 ml of water and2.55 g (0.044 mol) of potassium hydroxide at 20° C., while stirring.After the mixture had been stirred for 30 minutes, it was acidified withconcentrated hydrochloric acid to a pH of 1, and was filtered undersuction. The product was purified by boiling with 30 ml of water.

Yield: 2.1 g (51% of theory) of α-benzylaminocyclopropanecarboxylicacid.

Melting point: 209° C.

The compounds of the formula ##STR677## which are listed in Table 6which follows, were prepared in an analogous manner:

                  TABLE 6                                                         ______________________________________                                                                            Refractive                                                                    index n.sub.D.sup.20 ;                                                        melting point                                                           Yield (°C.) or boil-                     Example                       (% of ing point                                 No.    R.sup.18     R.sup.19  theory)                                                                             (°C./mbar)                         ______________________________________                                        VIII-8                                                                                ##STR678##  NHCHO     74    1.5079                                    VIII-9 O.sup.⊖ HN(C.sub.2 H.sub.5).sub.3.sup.⊕                                        NHCHO     85    1.4461                                    VIII-10                                                                              OC.sub.2 H.sub.5                                                                           NHCHO     71    110/0.1                                   VIII-11                                                                              NH.sub.2     NHCHO     70    145                                       VIII-12                                                                              OCH.sub.3    NH.sub.3.sup.⊕ Cl.sup.⊖                                                     81    180                                       VIII-13                                                                              OCH.sub.3    NH.sub.2  77    1.4491                                    VIII-14                                                                               ##STR679##  NH.sub.3.sup.⊕ Cl.sup.⊖                                                     51    92                                        VIII-15                                                                               ##STR680##  NH.sub.2  86    1.4849                                    VIII-16                                                                              O.sup.⊖ Na.sup.⊕                                                               NH.sub.2  97    216                                       VIII-17                                                                              OH           NH.sub.2  75    220                                       VIII-18                                                                              OC.sub.2 H.sub.5                                                                           NH.sub.3.sup.⊕ Cl.sup.⊖                                                     83    108                                       VIII-19                                                                              OC.sub.2 H.sub.5                                                                           NH.sub.2  75    1.4440                                    VIII-20                                                                              O.sup.⊖ K.sup.⊕                                                                NHCOCH.sub.3                                                                            82    246                                       VIII-21                                                                              OC.sub.2 H.sub.5                                                                           NHCOCH.sub.3                                                                            90    76                                        VIII-22                                                                              O(CH.sub.2).sub.7 CH.sub.3                                                                 NHCHO     95    1.4321                                    VIII-23                                                                              O(CH.sub.2).sub.7 CH.sub.3                                                                 NH.sub.3.sup.⊕ Cl.sup.⊖                                                     91    1.4429                                    VIII-24                                                                              O.sup.⊖ Na.sup.⊕                                                               NHCHO     90    221                                       ______________________________________                                    

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

We claim:
 1. A plant-growth-inhibiting composition comprising a plant growth-inhibiting effective amount of ##STR681## and 0.05 to 5 times its weight of ##STR682##
 2. A composition according to claim 1, wherein the second ingredient is present in about 0.1 to 4 times the weight of the first.
 3. A method of inhibiting the growth of plants which comprises applying to the plants, or to a habitat thereof, a plant growth-inhibiting effective amount of a composition according to claim
 1. 